S1

Electronic Supplementary Information

The seeming lack of CFbullbullbullHO intramolecular hydrogenbonds in linear aliphatic fluoroalcohols in solution

Rodrigo A Cormanich12 Roberto Rittner2 Matheus P Freitas3 and Michael Buumlhl1

1EastChem School of Chemistry University of St Andrews North Haugh St Andrews Fife KY16 9ST

UK

2 Chemistry Institute State University of Campinas PO Box 6154 13083-970 Campinas SP Brazil

3 Department of Chemistry Federal University of Lavras PO Box 3037 37200-000 Lavras MG Brazil

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is copy the Owner Societies 2014

S2

Synthesis of 4-fluorobutanol

1 Mono acylation

226 mmol (252 mL) of Acetic anhydride was added to a stirred solution of 14-butanediol (222 mmol 197 mL) and 1g of CeCl3 in 500 mL of THF under nitrogenatmosphere When judged complete by TLC (EtOAcpetroleum ether at 4060 ratio) thereaction was diluted with 200 mL of Et2O and washed twice with 50 mL of brine Theorganics were dried with MgSO4 and the solvent was evaporated obtaining 2 as a crudeproduct The product was purified via flash column chromatography (EtOAcpetrolether in 4060 ratio) to provide the pure mono-acetate 2 in 55 yield

2 DAST Fluorination

16119 mmol (1218 mL) of DAST was added dropwise to a stirred solution of 2 (3074mmol 393 mL) in 300 mL of dichloromethane under nitrogen atmosphere and at -78ordmC The reaction mixture was warmed up to RT and was allowed to react for 72h Theworkout was done by adding the reaction solution on water (50 mL) and extracted 3xwith EtOAc (100 mL) before use of MgSO4 as drying agent and careful solventevaporation since the product is volatile The fluorinated product 3 was obtained in81 yield after column chromatography (DCMEt2O in 5050 ratio)

3 LiAlH4 Reduction

OAc

F

LiAlH4

0ordm to RT Et2OOH

F

(3) (4)

828 mmol (314 g) of LiAlH4 was added carefully to a stirred solution of 3 (207 mmol295 mL) in 200 mL of Et2O at 0ordmC The reaction mixture was warmed up to RT and

S3

achieved completion after 1h as judged by TLC (100 Et2O) The workup followed theprocedure below

1- The solution was diluted with ether (100 mL) and cooled down to 0ordmC

2- It was slowly added 3 mL of H2O

3- It was added 3 mL of NaOH

4- It was added 10 mL of H2O

5- The mixture was warmed up to room temperature and stirred for 15 min

6- MgSO4 was added to the reaction mixture

7- The reaction mixture was filtered

The crude product 4 obtained in quantitative yield was purified by columnchromatograpy (100 Et2O) achieving 25 yield after careful solvent evaporation

4 Colourless liquid IR (003 M CCl4 solution) υcm-1 (T = 831medium) ~2962 cm-1

(T = 702 strong) ~2900 cm-1 (T = 798 strong) ~2877 cm-1 (T = 838 medium) ~1474 cm-1

(T = 933 weak) ~1445 cm-1 (T = 917 weak) ~1434 cm-1 (T = 930 weak) ~1388 cm-1 (T =

887 weak) ~1043 cm-1 (T = 651 strong) ~1008 cm-1 (T = 749 strong) ~ 977 cm-1 (T = 851

medium) ~945 cm-1 (T = 834 medium) 1H NMR (60017 MHz CD2Cl2 solution) δ 452 (2H dt 3JHF = 474 Hz 3JHH = 605 Hz) δ 369 (2H m) δ 181 (2H m) δ 169 (2H m) 13C (1509 MHz CD2Cl2

solution) δ 8352 (d 1JFC = 1635 Hz) δ 6273 (s) δ 2910 (d 3JFC = 501) 2751 (d 2JFC = 2001)

S4

(a) (b)

Figure S1 a) PES built by scanning the (H-O-C-C) and θ (F-C-C-O) dihedral angles of FE at the

B3LYPcc-pVDZ level b) Contour map in the plane of and θ dihedral angles

S5

1 2 3 4 5

Figure S2 Molecular graphs for FE conformers obtained with the QTAIM Green points represent

BCPs

S6

Table S1 Relative energies of FE conformer (kcal mol-1) obtained at different levels If nototherwise stated the aug-cc-pVDZ basis set was used

1 2 3 4 5

B3LYP 000 188 233 229 214

B3LYP-D3 000 210 247 239 228

B97D 000 216 229 234 258

MP2 000 205 258 238 219

MP2aug-cc-pVTZMP2aug-cc-pVDZ

000 196 246 234 217

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 203 245 224 214

S7

Table S2 Relative energies (E) of FE conformer obtained for MP2aug-cc-pVDZ optimisedgeometries Thermal corrections to enthalpes (H) and Gibbs free energies (G) were obtained fromB3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each caseEnergies and populations are given separately for isolated molecule and by using the implicit IEF-PCM implicit solvent model for acetonitrile dielectric constant value

Isolated

1 2 3 4 5

E (kcal mol-1) 000 205 258 219 238

P (E) 920 29 12 23 17

H (kcal mol-1) 000 192 243 240 220

P (H) 912 36 15 16 22

G (kcal mol-1) 000 178 227 216 192

P (G) 880 43 19 23 34

Acetonitrile

1 2 3 4 5

E (kcal mol-1) 000 059 072 185 210

P (E) 575 212 171 25 17

H (kcal mol-1) 000 055 069 195 215

P (H) 564 224 176 21 15

G (kcal mol-1) 000 058 071 183 194

P (G) 567 214 172 26 21

S8

1 2 3 4 5Figure S3 FE NCI plots The redgreen NCI surface indicates a repulsive interaction between F and the

OH group The figures were obtained with a reduced density gradient (RDG) value of 06 au and the blue-

green-red values ranging from -002 to 002

S9

1 2 3 4 5Figure S4 NBOs involved in CHCF (conformers 1-3) and COCF (conformers 4 and 5)

hyperconjugative interaction in FE (obtained at the B3LYPaug-cc-pVDZ level isosurface values 004 au)

S10

1 2 3

4 5 6

7 8 9

10 11 12Figure S5 Geometrical representations of the FP conformers obtained at the MP2aug-cc-pVDZ level

S11

Table S3 Relative energies of FP conformers (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was usedBHandHEPR-III and SOPPA(CCSD)EPR-III 1hJFH SSCCs values (Hz) obtained for MP2aug-cc-pVDZ geometries are also indicated in the table bottom

1 2 3 4 5 6 7 8 9 10 11 12

B3LYP 005 000 063 068 081 071 108 102 126 174 190 325

B3LYP-D3 000 019 065 080 110 106 128 130 154 219 227 366

B97D 000 034 045 068 119 106 114 111 129 212 200 344

MP2 017 000 061 081 100 108 140 141 165 228 246 366

MP2aug-cc-pVTZMP2aug-cc-pVDZ

017 000 056 078 095 102 131 133 156 214 231 356

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 002 044 070 094 098 119 120 144 207 215 347

1hJFH (BHandHEPR-III) -1267 -041 038 -032 -042 -050 -026 -019 -005 134 -077 -015

1hJFH [SOPPA(CCSD)EPR-III] -1139 -024 023 -005 -038 -040 006 -004 033 178 -061 -010

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S2

Synthesis of 4-fluorobutanol

1 Mono acylation

226 mmol (252 mL) of Acetic anhydride was added to a stirred solution of 14-butanediol (222 mmol 197 mL) and 1g of CeCl3 in 500 mL of THF under nitrogenatmosphere When judged complete by TLC (EtOAcpetroleum ether at 4060 ratio) thereaction was diluted with 200 mL of Et2O and washed twice with 50 mL of brine Theorganics were dried with MgSO4 and the solvent was evaporated obtaining 2 as a crudeproduct The product was purified via flash column chromatography (EtOAcpetrolether in 4060 ratio) to provide the pure mono-acetate 2 in 55 yield

2 DAST Fluorination

16119 mmol (1218 mL) of DAST was added dropwise to a stirred solution of 2 (3074mmol 393 mL) in 300 mL of dichloromethane under nitrogen atmosphere and at -78ordmC The reaction mixture was warmed up to RT and was allowed to react for 72h Theworkout was done by adding the reaction solution on water (50 mL) and extracted 3xwith EtOAc (100 mL) before use of MgSO4 as drying agent and careful solventevaporation since the product is volatile The fluorinated product 3 was obtained in81 yield after column chromatography (DCMEt2O in 5050 ratio)

3 LiAlH4 Reduction

OAc

F

LiAlH4

0ordm to RT Et2OOH

F

(3) (4)

828 mmol (314 g) of LiAlH4 was added carefully to a stirred solution of 3 (207 mmol295 mL) in 200 mL of Et2O at 0ordmC The reaction mixture was warmed up to RT and

S3

achieved completion after 1h as judged by TLC (100 Et2O) The workup followed theprocedure below

1- The solution was diluted with ether (100 mL) and cooled down to 0ordmC

2- It was slowly added 3 mL of H2O

3- It was added 3 mL of NaOH

4- It was added 10 mL of H2O

5- The mixture was warmed up to room temperature and stirred for 15 min

6- MgSO4 was added to the reaction mixture

7- The reaction mixture was filtered

The crude product 4 obtained in quantitative yield was purified by columnchromatograpy (100 Et2O) achieving 25 yield after careful solvent evaporation

4 Colourless liquid IR (003 M CCl4 solution) υcm-1 (T = 831medium) ~2962 cm-1

(T = 702 strong) ~2900 cm-1 (T = 798 strong) ~2877 cm-1 (T = 838 medium) ~1474 cm-1

(T = 933 weak) ~1445 cm-1 (T = 917 weak) ~1434 cm-1 (T = 930 weak) ~1388 cm-1 (T =

887 weak) ~1043 cm-1 (T = 651 strong) ~1008 cm-1 (T = 749 strong) ~ 977 cm-1 (T = 851

medium) ~945 cm-1 (T = 834 medium) 1H NMR (60017 MHz CD2Cl2 solution) δ 452 (2H dt 3JHF = 474 Hz 3JHH = 605 Hz) δ 369 (2H m) δ 181 (2H m) δ 169 (2H m) 13C (1509 MHz CD2Cl2

solution) δ 8352 (d 1JFC = 1635 Hz) δ 6273 (s) δ 2910 (d 3JFC = 501) 2751 (d 2JFC = 2001)

S4

(a) (b)

Figure S1 a) PES built by scanning the (H-O-C-C) and θ (F-C-C-O) dihedral angles of FE at the

B3LYPcc-pVDZ level b) Contour map in the plane of and θ dihedral angles

S5

1 2 3 4 5

Figure S2 Molecular graphs for FE conformers obtained with the QTAIM Green points represent

BCPs

S6

Table S1 Relative energies of FE conformer (kcal mol-1) obtained at different levels If nototherwise stated the aug-cc-pVDZ basis set was used

1 2 3 4 5

B3LYP 000 188 233 229 214

B3LYP-D3 000 210 247 239 228

B97D 000 216 229 234 258

MP2 000 205 258 238 219

MP2aug-cc-pVTZMP2aug-cc-pVDZ

000 196 246 234 217

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 203 245 224 214

S7

Table S2 Relative energies (E) of FE conformer obtained for MP2aug-cc-pVDZ optimisedgeometries Thermal corrections to enthalpes (H) and Gibbs free energies (G) were obtained fromB3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each caseEnergies and populations are given separately for isolated molecule and by using the implicit IEF-PCM implicit solvent model for acetonitrile dielectric constant value

Isolated

1 2 3 4 5

E (kcal mol-1) 000 205 258 219 238

P (E) 920 29 12 23 17

H (kcal mol-1) 000 192 243 240 220

P (H) 912 36 15 16 22

G (kcal mol-1) 000 178 227 216 192

P (G) 880 43 19 23 34

Acetonitrile

1 2 3 4 5

E (kcal mol-1) 000 059 072 185 210

P (E) 575 212 171 25 17

H (kcal mol-1) 000 055 069 195 215

P (H) 564 224 176 21 15

G (kcal mol-1) 000 058 071 183 194

P (G) 567 214 172 26 21

S8

1 2 3 4 5Figure S3 FE NCI plots The redgreen NCI surface indicates a repulsive interaction between F and the

OH group The figures were obtained with a reduced density gradient (RDG) value of 06 au and the blue-

green-red values ranging from -002 to 002

S9

1 2 3 4 5Figure S4 NBOs involved in CHCF (conformers 1-3) and COCF (conformers 4 and 5)

hyperconjugative interaction in FE (obtained at the B3LYPaug-cc-pVDZ level isosurface values 004 au)

S10

1 2 3

4 5 6

7 8 9

10 11 12Figure S5 Geometrical representations of the FP conformers obtained at the MP2aug-cc-pVDZ level

S11

Table S3 Relative energies of FP conformers (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was usedBHandHEPR-III and SOPPA(CCSD)EPR-III 1hJFH SSCCs values (Hz) obtained for MP2aug-cc-pVDZ geometries are also indicated in the table bottom

1 2 3 4 5 6 7 8 9 10 11 12

B3LYP 005 000 063 068 081 071 108 102 126 174 190 325

B3LYP-D3 000 019 065 080 110 106 128 130 154 219 227 366

B97D 000 034 045 068 119 106 114 111 129 212 200 344

MP2 017 000 061 081 100 108 140 141 165 228 246 366

MP2aug-cc-pVTZMP2aug-cc-pVDZ

017 000 056 078 095 102 131 133 156 214 231 356

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 002 044 070 094 098 119 120 144 207 215 347

1hJFH (BHandHEPR-III) -1267 -041 038 -032 -042 -050 -026 -019 -005 134 -077 -015

1hJFH [SOPPA(CCSD)EPR-III] -1139 -024 023 -005 -038 -040 006 -004 033 178 -061 -010

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S3

achieved completion after 1h as judged by TLC (100 Et2O) The workup followed theprocedure below

1- The solution was diluted with ether (100 mL) and cooled down to 0ordmC

2- It was slowly added 3 mL of H2O

3- It was added 3 mL of NaOH

4- It was added 10 mL of H2O

5- The mixture was warmed up to room temperature and stirred for 15 min

6- MgSO4 was added to the reaction mixture

7- The reaction mixture was filtered

The crude product 4 obtained in quantitative yield was purified by columnchromatograpy (100 Et2O) achieving 25 yield after careful solvent evaporation

4 Colourless liquid IR (003 M CCl4 solution) υcm-1 (T = 831medium) ~2962 cm-1

(T = 702 strong) ~2900 cm-1 (T = 798 strong) ~2877 cm-1 (T = 838 medium) ~1474 cm-1

(T = 933 weak) ~1445 cm-1 (T = 917 weak) ~1434 cm-1 (T = 930 weak) ~1388 cm-1 (T =

887 weak) ~1043 cm-1 (T = 651 strong) ~1008 cm-1 (T = 749 strong) ~ 977 cm-1 (T = 851

medium) ~945 cm-1 (T = 834 medium) 1H NMR (60017 MHz CD2Cl2 solution) δ 452 (2H dt 3JHF = 474 Hz 3JHH = 605 Hz) δ 369 (2H m) δ 181 (2H m) δ 169 (2H m) 13C (1509 MHz CD2Cl2

solution) δ 8352 (d 1JFC = 1635 Hz) δ 6273 (s) δ 2910 (d 3JFC = 501) 2751 (d 2JFC = 2001)

S4

(a) (b)

Figure S1 a) PES built by scanning the (H-O-C-C) and θ (F-C-C-O) dihedral angles of FE at the

B3LYPcc-pVDZ level b) Contour map in the plane of and θ dihedral angles

S5

1 2 3 4 5

Figure S2 Molecular graphs for FE conformers obtained with the QTAIM Green points represent

BCPs

S6

Table S1 Relative energies of FE conformer (kcal mol-1) obtained at different levels If nototherwise stated the aug-cc-pVDZ basis set was used

1 2 3 4 5

B3LYP 000 188 233 229 214

B3LYP-D3 000 210 247 239 228

B97D 000 216 229 234 258

MP2 000 205 258 238 219

MP2aug-cc-pVTZMP2aug-cc-pVDZ

000 196 246 234 217

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 203 245 224 214

S7

Table S2 Relative energies (E) of FE conformer obtained for MP2aug-cc-pVDZ optimisedgeometries Thermal corrections to enthalpes (H) and Gibbs free energies (G) were obtained fromB3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each caseEnergies and populations are given separately for isolated molecule and by using the implicit IEF-PCM implicit solvent model for acetonitrile dielectric constant value

Isolated

1 2 3 4 5

E (kcal mol-1) 000 205 258 219 238

P (E) 920 29 12 23 17

H (kcal mol-1) 000 192 243 240 220

P (H) 912 36 15 16 22

G (kcal mol-1) 000 178 227 216 192

P (G) 880 43 19 23 34

Acetonitrile

1 2 3 4 5

E (kcal mol-1) 000 059 072 185 210

P (E) 575 212 171 25 17

H (kcal mol-1) 000 055 069 195 215

P (H) 564 224 176 21 15

G (kcal mol-1) 000 058 071 183 194

P (G) 567 214 172 26 21

S8

1 2 3 4 5Figure S3 FE NCI plots The redgreen NCI surface indicates a repulsive interaction between F and the

OH group The figures were obtained with a reduced density gradient (RDG) value of 06 au and the blue-

green-red values ranging from -002 to 002

S9

1 2 3 4 5Figure S4 NBOs involved in CHCF (conformers 1-3) and COCF (conformers 4 and 5)

hyperconjugative interaction in FE (obtained at the B3LYPaug-cc-pVDZ level isosurface values 004 au)

S10

1 2 3

4 5 6

7 8 9

10 11 12Figure S5 Geometrical representations of the FP conformers obtained at the MP2aug-cc-pVDZ level

S11

Table S3 Relative energies of FP conformers (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was usedBHandHEPR-III and SOPPA(CCSD)EPR-III 1hJFH SSCCs values (Hz) obtained for MP2aug-cc-pVDZ geometries are also indicated in the table bottom

1 2 3 4 5 6 7 8 9 10 11 12

B3LYP 005 000 063 068 081 071 108 102 126 174 190 325

B3LYP-D3 000 019 065 080 110 106 128 130 154 219 227 366

B97D 000 034 045 068 119 106 114 111 129 212 200 344

MP2 017 000 061 081 100 108 140 141 165 228 246 366

MP2aug-cc-pVTZMP2aug-cc-pVDZ

017 000 056 078 095 102 131 133 156 214 231 356

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 002 044 070 094 098 119 120 144 207 215 347

1hJFH (BHandHEPR-III) -1267 -041 038 -032 -042 -050 -026 -019 -005 134 -077 -015

1hJFH [SOPPA(CCSD)EPR-III] -1139 -024 023 -005 -038 -040 006 -004 033 178 -061 -010

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S4

(a) (b)

Figure S1 a) PES built by scanning the (H-O-C-C) and θ (F-C-C-O) dihedral angles of FE at the

B3LYPcc-pVDZ level b) Contour map in the plane of and θ dihedral angles

S5

1 2 3 4 5

Figure S2 Molecular graphs for FE conformers obtained with the QTAIM Green points represent

BCPs

S6

Table S1 Relative energies of FE conformer (kcal mol-1) obtained at different levels If nototherwise stated the aug-cc-pVDZ basis set was used

1 2 3 4 5

B3LYP 000 188 233 229 214

B3LYP-D3 000 210 247 239 228

B97D 000 216 229 234 258

MP2 000 205 258 238 219

MP2aug-cc-pVTZMP2aug-cc-pVDZ

000 196 246 234 217

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 203 245 224 214

S7

Table S2 Relative energies (E) of FE conformer obtained for MP2aug-cc-pVDZ optimisedgeometries Thermal corrections to enthalpes (H) and Gibbs free energies (G) were obtained fromB3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each caseEnergies and populations are given separately for isolated molecule and by using the implicit IEF-PCM implicit solvent model for acetonitrile dielectric constant value

Isolated

1 2 3 4 5

E (kcal mol-1) 000 205 258 219 238

P (E) 920 29 12 23 17

H (kcal mol-1) 000 192 243 240 220

P (H) 912 36 15 16 22

G (kcal mol-1) 000 178 227 216 192

P (G) 880 43 19 23 34

Acetonitrile

1 2 3 4 5

E (kcal mol-1) 000 059 072 185 210

P (E) 575 212 171 25 17

H (kcal mol-1) 000 055 069 195 215

P (H) 564 224 176 21 15

G (kcal mol-1) 000 058 071 183 194

P (G) 567 214 172 26 21

S8

1 2 3 4 5Figure S3 FE NCI plots The redgreen NCI surface indicates a repulsive interaction between F and the

OH group The figures were obtained with a reduced density gradient (RDG) value of 06 au and the blue-

green-red values ranging from -002 to 002

S9

1 2 3 4 5Figure S4 NBOs involved in CHCF (conformers 1-3) and COCF (conformers 4 and 5)

hyperconjugative interaction in FE (obtained at the B3LYPaug-cc-pVDZ level isosurface values 004 au)

S10

1 2 3

4 5 6

7 8 9

10 11 12Figure S5 Geometrical representations of the FP conformers obtained at the MP2aug-cc-pVDZ level

S11

Table S3 Relative energies of FP conformers (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was usedBHandHEPR-III and SOPPA(CCSD)EPR-III 1hJFH SSCCs values (Hz) obtained for MP2aug-cc-pVDZ geometries are also indicated in the table bottom

1 2 3 4 5 6 7 8 9 10 11 12

B3LYP 005 000 063 068 081 071 108 102 126 174 190 325

B3LYP-D3 000 019 065 080 110 106 128 130 154 219 227 366

B97D 000 034 045 068 119 106 114 111 129 212 200 344

MP2 017 000 061 081 100 108 140 141 165 228 246 366

MP2aug-cc-pVTZMP2aug-cc-pVDZ

017 000 056 078 095 102 131 133 156 214 231 356

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 002 044 070 094 098 119 120 144 207 215 347

1hJFH (BHandHEPR-III) -1267 -041 038 -032 -042 -050 -026 -019 -005 134 -077 -015

1hJFH [SOPPA(CCSD)EPR-III] -1139 -024 023 -005 -038 -040 006 -004 033 178 -061 -010

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S5

1 2 3 4 5

Figure S2 Molecular graphs for FE conformers obtained with the QTAIM Green points represent

BCPs

S6

Table S1 Relative energies of FE conformer (kcal mol-1) obtained at different levels If nototherwise stated the aug-cc-pVDZ basis set was used

1 2 3 4 5

B3LYP 000 188 233 229 214

B3LYP-D3 000 210 247 239 228

B97D 000 216 229 234 258

MP2 000 205 258 238 219

MP2aug-cc-pVTZMP2aug-cc-pVDZ

000 196 246 234 217

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 203 245 224 214

S7

Table S2 Relative energies (E) of FE conformer obtained for MP2aug-cc-pVDZ optimisedgeometries Thermal corrections to enthalpes (H) and Gibbs free energies (G) were obtained fromB3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each caseEnergies and populations are given separately for isolated molecule and by using the implicit IEF-PCM implicit solvent model for acetonitrile dielectric constant value

Isolated

1 2 3 4 5

E (kcal mol-1) 000 205 258 219 238

P (E) 920 29 12 23 17

H (kcal mol-1) 000 192 243 240 220

P (H) 912 36 15 16 22

G (kcal mol-1) 000 178 227 216 192

P (G) 880 43 19 23 34

Acetonitrile

1 2 3 4 5

E (kcal mol-1) 000 059 072 185 210

P (E) 575 212 171 25 17

H (kcal mol-1) 000 055 069 195 215

P (H) 564 224 176 21 15

G (kcal mol-1) 000 058 071 183 194

P (G) 567 214 172 26 21

S8

1 2 3 4 5Figure S3 FE NCI plots The redgreen NCI surface indicates a repulsive interaction between F and the

OH group The figures were obtained with a reduced density gradient (RDG) value of 06 au and the blue-

green-red values ranging from -002 to 002

S9

1 2 3 4 5Figure S4 NBOs involved in CHCF (conformers 1-3) and COCF (conformers 4 and 5)

hyperconjugative interaction in FE (obtained at the B3LYPaug-cc-pVDZ level isosurface values 004 au)

S10

1 2 3

4 5 6

7 8 9

10 11 12Figure S5 Geometrical representations of the FP conformers obtained at the MP2aug-cc-pVDZ level

S11

Table S3 Relative energies of FP conformers (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was usedBHandHEPR-III and SOPPA(CCSD)EPR-III 1hJFH SSCCs values (Hz) obtained for MP2aug-cc-pVDZ geometries are also indicated in the table bottom

1 2 3 4 5 6 7 8 9 10 11 12

B3LYP 005 000 063 068 081 071 108 102 126 174 190 325

B3LYP-D3 000 019 065 080 110 106 128 130 154 219 227 366

B97D 000 034 045 068 119 106 114 111 129 212 200 344

MP2 017 000 061 081 100 108 140 141 165 228 246 366

MP2aug-cc-pVTZMP2aug-cc-pVDZ

017 000 056 078 095 102 131 133 156 214 231 356

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 002 044 070 094 098 119 120 144 207 215 347

1hJFH (BHandHEPR-III) -1267 -041 038 -032 -042 -050 -026 -019 -005 134 -077 -015

1hJFH [SOPPA(CCSD)EPR-III] -1139 -024 023 -005 -038 -040 006 -004 033 178 -061 -010

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S6

Table S1 Relative energies of FE conformer (kcal mol-1) obtained at different levels If nototherwise stated the aug-cc-pVDZ basis set was used

1 2 3 4 5

B3LYP 000 188 233 229 214

B3LYP-D3 000 210 247 239 228

B97D 000 216 229 234 258

MP2 000 205 258 238 219

MP2aug-cc-pVTZMP2aug-cc-pVDZ

000 196 246 234 217

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 203 245 224 214

S7

Table S2 Relative energies (E) of FE conformer obtained for MP2aug-cc-pVDZ optimisedgeometries Thermal corrections to enthalpes (H) and Gibbs free energies (G) were obtained fromB3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each caseEnergies and populations are given separately for isolated molecule and by using the implicit IEF-PCM implicit solvent model for acetonitrile dielectric constant value

Isolated

1 2 3 4 5

E (kcal mol-1) 000 205 258 219 238

P (E) 920 29 12 23 17

H (kcal mol-1) 000 192 243 240 220

P (H) 912 36 15 16 22

G (kcal mol-1) 000 178 227 216 192

P (G) 880 43 19 23 34

Acetonitrile

1 2 3 4 5

E (kcal mol-1) 000 059 072 185 210

P (E) 575 212 171 25 17

H (kcal mol-1) 000 055 069 195 215

P (H) 564 224 176 21 15

G (kcal mol-1) 000 058 071 183 194

P (G) 567 214 172 26 21

S8

1 2 3 4 5Figure S3 FE NCI plots The redgreen NCI surface indicates a repulsive interaction between F and the

OH group The figures were obtained with a reduced density gradient (RDG) value of 06 au and the blue-

green-red values ranging from -002 to 002

S9

1 2 3 4 5Figure S4 NBOs involved in CHCF (conformers 1-3) and COCF (conformers 4 and 5)

hyperconjugative interaction in FE (obtained at the B3LYPaug-cc-pVDZ level isosurface values 004 au)

S10

1 2 3

4 5 6

7 8 9

10 11 12Figure S5 Geometrical representations of the FP conformers obtained at the MP2aug-cc-pVDZ level

S11

Table S3 Relative energies of FP conformers (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was usedBHandHEPR-III and SOPPA(CCSD)EPR-III 1hJFH SSCCs values (Hz) obtained for MP2aug-cc-pVDZ geometries are also indicated in the table bottom

1 2 3 4 5 6 7 8 9 10 11 12

B3LYP 005 000 063 068 081 071 108 102 126 174 190 325

B3LYP-D3 000 019 065 080 110 106 128 130 154 219 227 366

B97D 000 034 045 068 119 106 114 111 129 212 200 344

MP2 017 000 061 081 100 108 140 141 165 228 246 366

MP2aug-cc-pVTZMP2aug-cc-pVDZ

017 000 056 078 095 102 131 133 156 214 231 356

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 002 044 070 094 098 119 120 144 207 215 347

1hJFH (BHandHEPR-III) -1267 -041 038 -032 -042 -050 -026 -019 -005 134 -077 -015

1hJFH [SOPPA(CCSD)EPR-III] -1139 -024 023 -005 -038 -040 006 -004 033 178 -061 -010

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S7

Table S2 Relative energies (E) of FE conformer obtained for MP2aug-cc-pVDZ optimisedgeometries Thermal corrections to enthalpes (H) and Gibbs free energies (G) were obtained fromB3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each caseEnergies and populations are given separately for isolated molecule and by using the implicit IEF-PCM implicit solvent model for acetonitrile dielectric constant value

Isolated

1 2 3 4 5

E (kcal mol-1) 000 205 258 219 238

P (E) 920 29 12 23 17

H (kcal mol-1) 000 192 243 240 220

P (H) 912 36 15 16 22

G (kcal mol-1) 000 178 227 216 192

P (G) 880 43 19 23 34

Acetonitrile

1 2 3 4 5

E (kcal mol-1) 000 059 072 185 210

P (E) 575 212 171 25 17

H (kcal mol-1) 000 055 069 195 215

P (H) 564 224 176 21 15

G (kcal mol-1) 000 058 071 183 194

P (G) 567 214 172 26 21

S8

1 2 3 4 5Figure S3 FE NCI plots The redgreen NCI surface indicates a repulsive interaction between F and the

OH group The figures were obtained with a reduced density gradient (RDG) value of 06 au and the blue-

green-red values ranging from -002 to 002

S9

1 2 3 4 5Figure S4 NBOs involved in CHCF (conformers 1-3) and COCF (conformers 4 and 5)

hyperconjugative interaction in FE (obtained at the B3LYPaug-cc-pVDZ level isosurface values 004 au)

S10

1 2 3

4 5 6

7 8 9

10 11 12Figure S5 Geometrical representations of the FP conformers obtained at the MP2aug-cc-pVDZ level

S11

Table S3 Relative energies of FP conformers (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was usedBHandHEPR-III and SOPPA(CCSD)EPR-III 1hJFH SSCCs values (Hz) obtained for MP2aug-cc-pVDZ geometries are also indicated in the table bottom

1 2 3 4 5 6 7 8 9 10 11 12

B3LYP 005 000 063 068 081 071 108 102 126 174 190 325

B3LYP-D3 000 019 065 080 110 106 128 130 154 219 227 366

B97D 000 034 045 068 119 106 114 111 129 212 200 344

MP2 017 000 061 081 100 108 140 141 165 228 246 366

MP2aug-cc-pVTZMP2aug-cc-pVDZ

017 000 056 078 095 102 131 133 156 214 231 356

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 002 044 070 094 098 119 120 144 207 215 347

1hJFH (BHandHEPR-III) -1267 -041 038 -032 -042 -050 -026 -019 -005 134 -077 -015

1hJFH [SOPPA(CCSD)EPR-III] -1139 -024 023 -005 -038 -040 006 -004 033 178 -061 -010

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S8

1 2 3 4 5Figure S3 FE NCI plots The redgreen NCI surface indicates a repulsive interaction between F and the

OH group The figures were obtained with a reduced density gradient (RDG) value of 06 au and the blue-

green-red values ranging from -002 to 002

S9

1 2 3 4 5Figure S4 NBOs involved in CHCF (conformers 1-3) and COCF (conformers 4 and 5)

hyperconjugative interaction in FE (obtained at the B3LYPaug-cc-pVDZ level isosurface values 004 au)

S10

1 2 3

4 5 6

7 8 9

10 11 12Figure S5 Geometrical representations of the FP conformers obtained at the MP2aug-cc-pVDZ level

S11

Table S3 Relative energies of FP conformers (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was usedBHandHEPR-III and SOPPA(CCSD)EPR-III 1hJFH SSCCs values (Hz) obtained for MP2aug-cc-pVDZ geometries are also indicated in the table bottom

1 2 3 4 5 6 7 8 9 10 11 12

B3LYP 005 000 063 068 081 071 108 102 126 174 190 325

B3LYP-D3 000 019 065 080 110 106 128 130 154 219 227 366

B97D 000 034 045 068 119 106 114 111 129 212 200 344

MP2 017 000 061 081 100 108 140 141 165 228 246 366

MP2aug-cc-pVTZMP2aug-cc-pVDZ

017 000 056 078 095 102 131 133 156 214 231 356

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 002 044 070 094 098 119 120 144 207 215 347

1hJFH (BHandHEPR-III) -1267 -041 038 -032 -042 -050 -026 -019 -005 134 -077 -015

1hJFH [SOPPA(CCSD)EPR-III] -1139 -024 023 -005 -038 -040 006 -004 033 178 -061 -010

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S9

1 2 3 4 5Figure S4 NBOs involved in CHCF (conformers 1-3) and COCF (conformers 4 and 5)

hyperconjugative interaction in FE (obtained at the B3LYPaug-cc-pVDZ level isosurface values 004 au)

S10

1 2 3

4 5 6

7 8 9

10 11 12Figure S5 Geometrical representations of the FP conformers obtained at the MP2aug-cc-pVDZ level

S11

Table S3 Relative energies of FP conformers (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was usedBHandHEPR-III and SOPPA(CCSD)EPR-III 1hJFH SSCCs values (Hz) obtained for MP2aug-cc-pVDZ geometries are also indicated in the table bottom

1 2 3 4 5 6 7 8 9 10 11 12

B3LYP 005 000 063 068 081 071 108 102 126 174 190 325

B3LYP-D3 000 019 065 080 110 106 128 130 154 219 227 366

B97D 000 034 045 068 119 106 114 111 129 212 200 344

MP2 017 000 061 081 100 108 140 141 165 228 246 366

MP2aug-cc-pVTZMP2aug-cc-pVDZ

017 000 056 078 095 102 131 133 156 214 231 356

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 002 044 070 094 098 119 120 144 207 215 347

1hJFH (BHandHEPR-III) -1267 -041 038 -032 -042 -050 -026 -019 -005 134 -077 -015

1hJFH [SOPPA(CCSD)EPR-III] -1139 -024 023 -005 -038 -040 006 -004 033 178 -061 -010

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S10

1 2 3

4 5 6

7 8 9

10 11 12Figure S5 Geometrical representations of the FP conformers obtained at the MP2aug-cc-pVDZ level

S11

Table S3 Relative energies of FP conformers (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was usedBHandHEPR-III and SOPPA(CCSD)EPR-III 1hJFH SSCCs values (Hz) obtained for MP2aug-cc-pVDZ geometries are also indicated in the table bottom

1 2 3 4 5 6 7 8 9 10 11 12

B3LYP 005 000 063 068 081 071 108 102 126 174 190 325

B3LYP-D3 000 019 065 080 110 106 128 130 154 219 227 366

B97D 000 034 045 068 119 106 114 111 129 212 200 344

MP2 017 000 061 081 100 108 140 141 165 228 246 366

MP2aug-cc-pVTZMP2aug-cc-pVDZ

017 000 056 078 095 102 131 133 156 214 231 356

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 002 044 070 094 098 119 120 144 207 215 347

1hJFH (BHandHEPR-III) -1267 -041 038 -032 -042 -050 -026 -019 -005 134 -077 -015

1hJFH [SOPPA(CCSD)EPR-III] -1139 -024 023 -005 -038 -040 006 -004 033 178 -061 -010

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S11

Table S3 Relative energies of FP conformers (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was usedBHandHEPR-III and SOPPA(CCSD)EPR-III 1hJFH SSCCs values (Hz) obtained for MP2aug-cc-pVDZ geometries are also indicated in the table bottom

1 2 3 4 5 6 7 8 9 10 11 12

B3LYP 005 000 063 068 081 071 108 102 126 174 190 325

B3LYP-D3 000 019 065 080 110 106 128 130 154 219 227 366

B97D 000 034 045 068 119 106 114 111 129 212 200 344

MP2 017 000 061 081 100 108 140 141 165 228 246 366

MP2aug-cc-pVTZMP2aug-cc-pVDZ

017 000 056 078 095 102 131 133 156 214 231 356

CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ

000 002 044 070 094 098 119 120 144 207 215 347

1hJFH (BHandHEPR-III) -1267 -041 038 -032 -042 -050 -026 -019 -005 134 -077 -015

1hJFH [SOPPA(CCSD)EPR-III] -1139 -024 023 -005 -038 -040 006 -004 033 178 -061 -010

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S12

1 2 3 4 5 6 7 8 9 10 11 12

-14

-12

-10

-8

-6

-4

-2

0

2

BHandHEPR-IIISOPPA(CCSD)EPR-III

1hJ

FH

(Hz)

Conformer

Figure S6 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FP conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 029 Hz

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S13

Table S4 Relative energies (E)of FP conformer obtained for MP2aug-cc-pVDZ optimised geometries Thermal corrections to enthalpes (H) and Gibbs freeenergies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case Energies and populations aregiven separately for the isolated molecule and by using the implicit IEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant value

1 2 3 4 5 6 7 8 9 10 11 12

E 017 000 061 081 100 108 140 141 165 228 246 366

P (E) 252 333 119 85 62 53 31 31 21 07 05 01

Isolated H 022 000 065 080 104 109 142 141 164 234 251 352

P (H) 237 346 116 90 59 55 31 32 22 07 05 01

G 055 000 056 083 094 096 127 126 151 205 221 339

P (G) 140 357 139 88 73 71 42 42 28 11 08 01

E 011 000 058 060 085 091 114 113 132 195 208 310

P (E) 236 286 108 103 69 62 42 42 31 11 09 02

Cyclohexane H 019 000 061 060 090 092 118 117 133 202 214 298

P (H) 220 301 107 109 66 63 41 42 32 10 08 02

G 053 000 054 063 080 082 102 106 123 175 183 284

P (G) 126 308 125 106 80 77 55 51 39 16 14 03

E 001 000 053 023 066 066 084 080 081 148 157 214

P (E) 211 215 88 146 70 70 52 56 54 18 15 06

CH2Cl2 H 008 000 055 024 072 068 088 084 086 158 166 205

P (H) 197 227 90 151 67 71 51 55 54 16 14 07

G 041 000 049 026 061 058 071 075 077 130 134 198

P (G) 114 226 99 147 81 85 68 64 61 25 23 08

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S14

1 2 3

4 5 6

7 8 9

10 11 12Figure S7 Molecular graphs of FP conformers obtained with the QTAIM Green points represent BCPs

for conformer 1 the red point denotes a RCP

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S15

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S8 Geometrical representations of the FB conformers

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S16

Table S5 Relative energies of FB conformer (kcal mol-1) obtained at different levels If not otherwise stated the aug-cc-pVDZ basis set was used1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

B3LYP012 239 248 195 201 215 193 204 185 168 182 178 174 170 161 170 142 153 130

B3LYP-D3000 248 236 191 211 254 209 242 216 206 228 200 194 196 190 172 158 171 158

B97D014 182 229 129 186 205 171 192 163 176 199 176 164 180 144 158 162 179 154

MP2017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

MP2aug-cc-pVTZMP2aug-cc-

pVDZ012 232 222 171 204 238 187 224 195 177 204 199 191 151 170 175 137 142 148

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ006 236 216 179 207 241 195 228 201 190 216 197 191 171 174 176 150 156 156

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

B3LYP134 114 120 125 127 110 095 096 089 076 081 078 066 066 070 053 057 038 000

B3LYP-D3167 162 159 102 143 174 101 152 120 141 153 135 114 075 126 090 010 076 047

B97D127 142 118 089 154 146 064 127 087 136 147 139 122 063 104 079 000 064 059

MP2163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

MP2aug-cc-pVTZMP2aug-cc-

pVDZ150 140 135 103 128 146 064 131 100 113 119 094 081 019 103 076 000 058 011

CCSD(T)aug-cc-pVTZMP2aug-cc-

pVDZ155 148 143 102 140 153 077 136 107 127 133 114 101 045 110 084 000 067 033

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S17

Table S6 MP2aug-cc-pVDZ calculated populations () and dipole moments (μ) of FB conformers obtained for the isolated molecule and by using the implicitIEF-PCM implicit solvent model for cyclohexane and dichloromethane dielectric constant values BHandHEPR-III calculated 1hJFH SSCCs obtained for isolatedMP2aug-cc-pVDZ geometries are also indicated (in Hz) Calculated SOPPA(CCSD)EPR-III 1hJFH SSCC values for conformers 1 3 23 and 36 are shown inparenthesis (Hz)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Isolated

P119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

μ 34 18 37 16 34 18 35 19 35 29 21 32 35 37 18 37 14 36 13

1hJFH-3026

(-2258)009

(039)-1724

(-1204)-019(007)

121(135)

-026(-019)

-006(-011)

-001(-004)

-007(-019)

-005(-015)

036(024)

-023(-027)

195(125)

-019(-023)

002(006)

-063(-048)

-001(-003)

-007(-026)

-011(-025)

Cyclohexane

P109 04 --- 10 05 04 10 05 08 10 07 07 08 14 11 11 12 12 14

μ 384 199 --- 179 386 192 385 200 380 330 222 354 385 400 195 396 173 389 151

CH2Cl2

P68 06 --- 12 07 07 12 08 12 13 09 08 11 14 12 11 09 08 12

μ 442 219 --- 203 454 211 425 214 427 383 241 401 429 440 217 432 237 437 172

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Isolated

P10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

μ 33 35 18 23 39 18 24 33 16 33 22 37 35 16 17 19 34 17 21

1hJFH -008(-001)

-014(-010)

003(012)

-093(012)

007(000)

-027(-021)

030(011)

-008(-009)

-018(-005)

-005(-023)

105(082)

001(-012)

-016(-034)

010(-000)

013(009)

002(005)

-1199(-826)

-032(-025)

055(026)

Cyclohexane

P17 19 20 19 19 17 55 24 35 29 25 34 43 93 35 49 139 66 118

μ 367 383 203 249 417 192 255 362 176 368 229 396 381 177 189 212 383 183 226

CH2Cl2

P26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

μ 418 425 226 279 450 211 278 410 201 417 244 438 432 191 215 241 432 208 240

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S18

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38

-35

-30

-25

-20

-15

-10

-5

0

5

BHandHEPR-IIISOPPA(CCSD)EPR-III

Conformer

1hJ

FH

(Hz)

Figure S9 Comparison between SOPPA(CCSD)EPR-III and BHandHEPR-III calculated 1hJFH SSCC

values for FB conformers BHandHEPR-III 1hJFH mean absolute deviation (MAD) from 1hJFH

SOPPA(CCSD)EPR-III is of 058 Hz

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S19

Table S7 Relative energies (E) of FB conformers obtained for MP2aug-cc-pVDZ optimised geometries for the isolated molecule Thermal corrections to enthalpes (H) andGibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E017 248 239 182 212 253 193 240 207 183 216 211 202 159 180 181 146 149 155

P (E)119 02 03 07 04 02 06 03 05 07 04 04 05 11 08 08 13 13 12

H015 239 231 173 199 246 187 234 200 175 209 197 188 155 176 169 132 139 142

P (H)107 02 03 07 05 02 06 03 05 07 04 05 06 10 07 08 15 13 12

G096 219 266 168 212 237 170 227 191 154 199 196 202 141 166 191 130 154 154

P (G)34 04 02 10 05 03 10 04 07 13 06 06 06 16 10 07 19 13 13

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E163 158 157 106 133 171 064 149 114 128 140 111 089 020 121 086 000 068 019

P (E)10 11 11 27 17 09 54 13 23 18 15 24 36 114 21 37 159 50 115

H144 144 147 103 121 163 059 133 095 112 132 098 070 025 107 072 002 048 000

P (H)12 12 11 24 18 09 51 15 28 21 15 27 42 91 23 41 134 61 138

G142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142

P (G)15 18 16 20 20 14 75 20 38 31 23 42 48 77 31 42 38 76 170

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S20

Table S8 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using the cyclohexanedielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculations Conformerpopulations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E015 209 --- 153 192 206 158 192 167 153 178 178 166 136 148 151 145 147 135

P (E)97 04 --- 09 05 04 09 05 07 09 06 06 08 13 10 10 11 10 13

H026 214 --- 159 192 213 169 201 173 161 184 175 165 148 155 154 140 148 133

P (H)82 02 --- 09 05 040 07 04 07 09 06 07 08 11 09 10 12 11 14

G111 226 --- 181 214 219 183 212 176 174 194 192 190 166 163 187 159 178 158

P (G)26 04 --- 08 05 04 08 05 09 09 06 06 07 10 11 07 12 08 12

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E124 116 116 117 117 123 055 105 081 093 102 083 070 024 082 062 000 044 010

P (E)15 17 17 17 17 16 49 21 32 26 22 31 38 83 31 44 124 59 106

H118 115 119 120 115 127 065 104 074 088 106 081 060 036 080 058 015 036 000

P (H)18 19 17 17 18 15 43 22 37 29 21 33 47 70 33 48 99 70 128

G111 122 159 136 112 089 109 076 091 092 077 066 069 080 067 097 037 000 111

P (G)23 26 21 11 17 25 37 27 47 36 36 45 55 53 43 54 32 90 168

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S21

Table S9 Relative energies (E) of FB conformer obtained for MP2aug-cc-pVDZ optimised geometries for the IEF-PCM implicit solvent model using thedichloromethane dielectric constant value Thermal corrected enthalpy (H) and Gibbs free energies (G) were obtained from B3LYPaug-cc-pVDZ frequency calculationsConformer populations (P) are given for each case

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

E012 159 --- 112 149 149 114 137 112 108 132 136 119 105 112 119 132 138 113

P (E)67 06 --- 12 07 07 12 08 13 13 09 08 11 14 12 11 09 08 12

H008 151 --- 097 132 144 113 135 106 101 126 120 105 104 105 108 115 120 096

P (H)66 06 --- 15 08 07 11 08 13 14 09 10 13 13 13 12 11 10 15

G126 190 --- 137 187 183 160 180 142 144 171 173 161 153 143 173 183 168 153

P (G)16 05 --- 13 06 06 09 06 12 12 07 07 09 10 12 07 06 08 10

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

E068 061 070 125 107 065 047 048 042 044 060 049 036 032 039 033 000 015 001

P (E)26 30 25 10 14 27 37 37 40 39 30 36 45 48 43 47 82 64 80

H049 046 061 110 090 058 090 058 041 034 020 026 050 033 011 026 022 013 000

P (H)33 34 27 12 16 28 16 28 38 42 54 49 32 43 62 48 51 60 75

G325 360 267 075 115 360 259 393 566 478 427 449 582 287 515 584 192 870 1310

P (G)32 36 27 08 11 36 26 39 57 48 43 45 58 29 51 58 19 87 131

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S22

Table S10 Mean absolute deviations (MADs) over all respective conformers from the CCSD(T)aug-cc-pVTZMP2aug-cc-pVDZ theoretical level Valuesare given in kcal mol-1

FE FP FB Total

B3LYPaug-cc-pVDZ 006 016 022 044

B3LYP-D3aug-cc-pVDZ 008 013 013 034

B97Daug-cc-pVDZ 017 009 018 044

MP2aug-cc-pVDZ 007 016 008 031

MP2aug-cc-pVTZMP2aug-cc-pVDZ

004 010 009 023

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S23

1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 1920

21 22 23 24 25 26 27 28 29 30

31 32 33 34 35 36 37 38

Figure S10 Molecular graphs of FB conformer obtained with the QTAIM Green and points represent BCPs and RCPs respectively

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S24

Conformer 1

Conformer 3

Conformer 23

Conformer 36

Figure S11 NCI representations and RDG vs sign(λ2)ρ plots of FB conformers which have appropriate

geometry to form a CFHO intramolecular hydrogen bond The NCI plot were obtained with a reduced

density gradient (RDG) value of 05 and the blue-green-red values ranging from -002 to 001 au

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S25

NMR Spectra

Spectrum S1 1H NMR spectrum of FE in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME Fet_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1425INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 32DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1500 usecSI 131072SF 6001700267 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

435 ppm4285

4293

4300

4365

4372

4380

ppm

3630

3637

3644

3676

3684

3691

16 ppm

1582

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S26

Spectrum S2 19F NMR spectrum of FE in cyclohexane-d12

-22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME Fet_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT C6D12NS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S27

Spectrum S3 19H NMR spectrum of FE in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

3

19

9

20

0

NAME 2-FE-cd2cl2EXPNO 1PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722504 MHzNUC1 1HP1 1175 usecSI 131072SF 4998700241 MHzWDW EMSSB 0LB 030 HzGB 0PC 100450455 ppm

4443

4452

4460

4539

4547

4555

38 ppm

3774

3782

3790

3834

3842

3850

20 ppm

1932

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S28

Spectrum S4 19F NMR spectrum of FE in CD2Cl2

-22680 -22685 -22690 -22695 -22700 -22705 -22710 ppm

-22713

-22706

-22702

-22700

-22696

-22692

-22690

-22686

-22680 NAME 2-FE-cd2cl2

EXPNO 2PROCNO 1Date_ 20140219Time 1205INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 1DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702409641 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S29

Spectrum S5 1H NMR spectrum of FE in CD3CN

50 45 40 35 30 25 20 15 10 05 00 ppm

09

4

20

1

20

0

NAME FOH_CD3CNEXPNO 2PROCNO 1Date_ 20120425Time 1717INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 12335526 HzFIDRES 0188225 HzAQ 26564426 secRG 32DW 40533 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1000 usecSI 131072SF 6001700174 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

445 ppm

4385

4392

4399

4465

4472

4479

370 ppm

3659

3666

3673

3710

3717

3724

3031 ppm

3033

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S30

Spectrum S6 1H NMR spectrum of FE in CD3CN

-22810 -22815 -22820 -22825 -22830 -22835 -22840 ppm

-22841

-22836

-22832

-22831

-22827

-22824

-22822

-22819

-22814 NAME FOH_CD3CN

EXPNO 3PROCNO 1Date_ 20120710Time 1712INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 32768SOLVENT CD3CNNS 32DS 4SWH 1231527 HzFIDRES 0037583 HzAQ 133038578 secRG 203DW 406000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S31

Spectrum S7 1H NMR spectrum of FP in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

5

19

4

18

6

18

7

NAME Fprop_C6D12EXPNO 1PROCNO 1Date_ 20120710Time 1728INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT C6D12NS 8DS 0SWH 6602113 HzFIDRES 0100740 HzAQ 49633098 secRG 203DW 75733 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 1800 usecSI 131072SF 6001700261 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

445450 ppm

4400

4410

4419

4479

4489

4498

180 ppm

1760

1770

1779

1789

1799

1803

1812

1822

1832

1841

ppm

1024

370 ppm

3676

3686

3696

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S32

Spectrum S8 19F NMR spectrum of FP in cyclohexane-d12

-22315 -22320 -22325 -22330 -22335 ppm

-22340

-22336

-22332

-22331

-22327

-22323

-22323

-22319

-22314 NAME Fprop_C6D12

EXPNO 3PROCNO 1Date_ 20120710Time 1733INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zgflqnTD 65536SOLVENT C6D12NS 32DS 4SWH 4290618 HzFIDRES 0065470 HzAQ 76371784 secRG 203DW 116533 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 2500 usecSI 131072SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S33

Spectrum S9 1H NMR spectrum of FP in CD2Cl2

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

12

0

19

8

19

7

20

0

NAME 2-FE-testEXPNO 1PROCNO 1Date_ 20140219Time 1359INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 5494505 HzFIDRES 0083839 HzAQ 59638262 secRG 128DW 91000 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4998722472 MHzNUC1 1HP1 1175 usecSI 65536SF 4998691839 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

46 ppm

4512

4524

4535

4607

4618

4630

375 ppm3734

3746

3758

164 ppm

1639

190195 ppm

1862

1874

1886

1898

1910

1915

1927

1939

1951

1963

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S34

Spectrum S10 19F NMR spectrum of FP in CD2Cl2

-22200 -22205 -22210 -22215 -22220 -22225 ppm

-22229

-22223

-22219

-22218

-22213

-22209

-22208

-22203

-22198 NAME 2-FE-test

EXPNO 2PROCNO 1Date_ 20140219Time 1400INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 128DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 322DW 13333 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702442565 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S35

Spectrum S11 1H NMR spectrum of FB in cyclohexane-d12

75 70 65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

20

620

6

11

2

20

0

20

1

43 ppm

4258

4270

4281

4353

4365

4377

160165170175 ppm

1553

1555

1568

1573

1580

1585

1593

1597

1609

1647

1658

1663

1669

1675

1681

1686

1689

1696

1701

1708

1712

1719

1724

1731

1737

1750

355 ppm

3543

3556

3568

ppm

2285

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S36

Spectrum S12 19F NMR spectrum of FB in cyclohexane-d12

-21805 -21810 -21815 -21820 -21825 -21830 ppm

-21835

-21829

-21825

-21824

-21819

-21815

-21814

-21809

-21804 NAME 4-FB_cyclohex

EXPNO 2PROCNO 1Date_ 20140208Time 1148INSTRUM spectPROBHD 5 mm PABBO BBPULPROG zgflqnTD 131072SOLVENT AcetoneNS 64DS 4SWH 37500000 HzFIDRES 0286102 HzAQ 17476766 secRG 203DW 13333 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 4702451972 MHzNUC1 19FP1 1650 usecSI 65536SF 4703477330 MHzWDW EMSSB 0LB 000 HzGB 0PC 100

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S37

Spectrum S13 1H NMR spectrum of FB in CD2Cl2

65 60 55 50 45 40 35 30 25 20 15 10 05 00 ppm

09

8

19

51

98

19

4

20

0

NAME 4-FB_CD2CL2_05mgEXPNO 1PROCNO 1Date_ 20140211Time 1204INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 256DS 0SWH 4789272 HzFIDRES 0073078 HzAQ 68420086 secRG 203DW 104400 usecDE 650 usecTE 2982 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 6001718054 MHzNUC1 1HP1 738 usecSI 131072SF 6001700242 MHzWDW EMSSB 0LB 000 HzGB 0PC 100175180 ppm

1729

1733

1738

1743

1753

1755

1762

1772

1775

1781

1785

1797

165 ppm

1618

1629

1634

1640

1644

1651

1651

1654

1665

ppm

1352

1361

1371

ppm

3632

3642

3652

3662

45 ppm

4418

4428

4438

4497

4507

4517

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S38

Spectrum S14 19F NMR spectrum of FB in CD2Cl2

-21795 -21800 -21805 -21810 -21815 ppm

-21821

-21816

-21812

-21812

-21808

-21804

-21803

-21799

-21795 NAME 4-FB_CD2CL2_05mg

EXPNO 2PROCNO 1Date_ 20140211Time 1221INSTRUM spectPROBHD 5 mm TBI 1H13PULPROG zgflqnTD 131072SOLVENT CD2Cl2NS 256DS 0SWH 22727273 HzFIDRES 0173395 HzAQ 28836341 secRG 203DW 22000 usecDE 650 usecTE 2981 KD1 100000000 secTD0 1

======== CHANNEL f1 ========SFO1 5646009162 MHzNUC1 19FP1 2977 usecSI 65536SF 5647240260 MHzWDW EMSSB 0LB 030 HzGB 0PC 100

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S39

Infrared spectra

Spectrum S15 Infrared spectrum of FE in CCl4 Concentration = 001M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S40

Spectrum S16 Infrared spectrum of FE in CCl4 Concentration = 003M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S41

Spectrum S17 Infrared spectrum of FE in CCl4 Concentration = 005M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S42

Spectrum S18 Infrared spectrum of FE in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S43

Spectrum S19 Infrared spectrum of FP in CCl4 Concentration = 001M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S44

Spectrum S20 Infrared spectrum of FP in CCl4 Concentration = 003M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S45

Spectrum S21 Infrared spectrum of FP in CCl4 Concentration = 005M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S46

Spectrum S22 Infrared spectrum of FP in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S47

Spectrum S23 Infrared spectrum of FB in CCl4 Concentration = 001M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S48

Spectrum S24 Infrared spectrum of FB in CCl4 Concentration = 003M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S49

Spectrum S25 Infrared spectrum of FB in CCl4 Concentration = 005M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M

S50

Spectrum S26 Infrared spectrum of FB in CCl4 Concentration = 01M