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Electronic Supplementary Information
Elucidation of Ac-Gly-NHMe conformational preferences insolution
R. A. Cormanich,a,b R. Rittner*,b and M. Bühl*,a
a EastChem School of Chemistry, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST,
UK
b Chemistry Institute, State University of Campinas, P.O. Box 6154, 13083-970, Campinas, SP, Brazil
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015
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(a) (d)
(b) (e)
(c) (f)
Figure S1: Potential energy surface of (a) Ac-Gly-NHMe, (b) CF3-C(O)-Gly-NHMe and (c) Ac-Gly-N(Me)2, built
by scanning its and dihedral angles at the B3LYP/cc-pVDZ level. PES Ramachandran-like and dihedral
angles projection of (d) Ac-Gly-NHMe, (e) CF3-C(O)-Gly-NHMe and (f) Ac-Gly-N(Me)2.
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Ac-Gly-NHMe
1a 1b 1c 1d 1e
1f 1g 1h 1i 1j
1k
CF3-C(O)-Gly-NHMe
2a 2b 2c 2d 2e
2f 2g 2h 2i
Ac-Gly-N(Me)2
3a 3b 3c 3d 3e
3f 3gFigure S2: Compounds 1, 2 and 3 conformer geometrical representations.
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Table S1: Relative energies and mean absolute deviation (MAD) from the CCSD(T)-F12a/VDZ-F12//B3LYP/aug-cc-pVDZ in kcal mol-1 for compound 1conformers optimised geometries at different levels. DFT and DFT-D3 (showed in parenthesis) functionals used the aug-cc-pVDZ basis set. MP2/aug-cc-pVDZlevel was the only ab initio optimisation. Ab initio single point calculations were calculated on B3LYP/aug-cc-pVDZ optimised geometries.
1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k MAD
AM1 0.00 1.88 2.04 --- 2.99 2.21 5.29 --- 4.87 4.98 3.56 3.13
Semiepirical PM3 2.61 0.63 2.59 2.92 3.90 0.00 2.68 --- 3.37 2.19 2.03 3.97
PM6 0.00 2.05 2.22 --- 3.12 1.08 5.64 3.12 5.82 3.73 3.73 3.19
B3LYP 0.00 (0.00) 0.28 (1.27) 1.90 (2.53) 2.21 (2.77) 3.84 (3.52) 4.50 (4.33) 4.89 (5.48) 6.43 (6.38) 6.63 (6.83) 8.78 (8.26) 9.40 (8.29) 1.38 (1.30)
BLYP 0.00 (0.00) 1.59 (1.74) 2.08 (2.81) 2.17 (1.54) 3.80 (3.41) 4.35 (4.13) 4.85 (5.53) 6.33 (6.38) 6.49 (6.71) 8.69 (8.08) 9.15 (7.75) 1.38 (1.54)
DFT (DFT-D3) BP86 0.00 (0.00) 0.50 (1.89) 2.09 (2.87) 2.06 (---) 3.62 (3.24) 4.59 (4.42) 4.93 (5.67) 6.50 (6.51) 6.42 (6.72) 8.85 (8.30) 9.40 (8.00) 1.37 (1.37)
B97-D 0.00 (0.00) 1.84 (1.48) 2.57 (2.46) --- (---) 2.86 (2.96) 3.77 (4.15) 5.34 (5.22) 5.90 (6.14) 6.13 (6.30) 7.32 (7.76) 6.96 (7.59) 2.04 (1.85)
M06 0.00 (0.00) 0.25 (0.40) 1.40 (1.50) --- (---) 3.12 (2.99) 4.02 (3.93) 4.35 (4.47) 5.66 (5.64) 5.60 (5.64) 7.50 (7.44) 7.71 (7.41) 2.22 (2.23)
MP2/aug-cc-pVDZ* 0.00 (0.00) 1.75 (1.37) 3.18 (2.99) --- 3.46 (3.70) 4.33 (4.79) 6.12 (5.93) 6.38 (6.72) 7.64 (7.66) 8.45 (8.94) 8.28 (9.11) 1.40 (0.92)
RHF 0.73 0.00 2.09 2.40 4.64 4.90 5.35 6.53 7.86 9.12 10.41 1.04
DF-MP2 0.00 1.51 3.05 2.67 3.99 4.89 5.88 6.78 7.69 9.06 9.43 0.87
Ab initio DF-MP2-F12 0.00 1.24 2.84 2.61 3.97 4.88 5.82 6.82 7.61 9.19 9.66 0.85
SCS-DF-MP2 0.00 1.29 2.89 2.59 4.02 4.67 5.59 6.54 7.54 8.79 9.21 0.99
SCS-DF-MP2-F12/3C(FIX) 0.00 1.02 2.68 2.52 3.99 4.64 5.54 6.59 7.47 8.93 9.44 1.02
CCSD-F12a 0.00 0.72 2.42 2.50 4.07 4.61 5.41 6.42 7.34 8.81 9.51 1.11
CCSD(T)-F12a 0.00 1.26 3.89 3.76 5.26 5.75 6.88 7.74 8.68 10.15 10.65 ---
* MP2/aug-cc-pVTZ//MP2/aug-cc-pVDZ energy and MAD values are showed in parenthesis.
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Table S2: Compounds 1, 2 and 3 relative energies (ΔE) in kcal mol-1 and corresponding populations (%P) obtained at the B3LYP-D3/aug-cc-pVDZ level for theisolated compounds and by using the IEF-PCM implicit solvent model with dichloromethane, acetone, acetonitrile, DMSO, methanol and water dielectricconstants.
1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
ΔE %P ΔE %P ΔE %P ΔE %P ΔE %P ΔE %P ΔE %P ΔE %P ΔE %P ΔE %P ΔE %P
Isolated 0.00 87.4 1.27 10.3 2.53 1.2 2.77 0.8 3.52 0.2 4.33 0.1 5.48 0.0 6.38 0.0 6.83 0.0 8.26 0.0 8.29 0.0
CH2Cl2 0.00 56.2 0.65 18.9 1.77 2.8 0.64 19.2 1.88 2.4 4.19 0.0 3.12 0.3 3.48 0.2 4.22 0.0 5.03 0.0 6.26 0.0
Acetone 0.00 44.7 0.57 17.1 1.72 2.4 0.20 31.9 1.66 2.7 2.96 0.3 2.74 0.4 3.00 0.3 3.88 0.1 4.56 0.0 6.03 0.0
1 Acetonitrile 0.00 39.9 0.54 16.0 1.71 2.2 0.03 37.9 1.59 2.7 2.85 0.3 2.61 0.5 2.82 0.3 3.77 0.1 4.39 0.0 5.95 0.0
DMSO 0.03 38.3 0.56 15.6 1.73 2.1 0.00 40.0 1.59 2.7 2.83 0.3 2.59 0.5 2.79 0.4 3.75 0.1 4.37 0.0 5.95 0.0
Methanol 0.00 40.5 0.54 16.2 1.71 2.3 0.05 37.1 1.60 2.7 2.86 0.3 2.63 0.5 2.85 0.3 3.78 0.1 4.42 0.0 5.96 0.0
Water 0.10 36.1 0.62 15.0 1.80 2.0 0.00 42.8 1.63 2.7 2.85 0.3 2.61 0.5 2.79 0.4 3.78 0.1 4.37 0.0 5.99 0.0
2a 2b 2c 2d 2e 2f 2g 2h 2i
Isolated 0.00 47.7 0.01 47.3 1.35 4.9 --- --- 4.10 0.0 4.04 0.1 5.13 0.0 5.37 0.0 7.84 0.0 --- --- --- ---
CH2Cl2 0.95 13.7 0.00 68.0 1.24 8.4 1.16 9.6 3.92 0.1 4.07 0.1 4.40 0.0 5.04 0.0 5.42 0.0 --- --- --- ---
Acetone 1.06 11.1 0.00 66.2 1.29 7.5 0.88 14.9 3.88 0.1 4.05 0.1 4.26 0.1 5.03 0.0 4.94 0.0 --- --- --- ---
2 Acetonitrile 1.10 10.2 0.00 64.7 1.31 7.1 0.76 17.8 3.87 0.1 4.04 0.1 4.20 0.1 5.03 0.0 4.75 0.0 --- --- --- ---
DMSO 1.11 9.8 0.00 64.1 1.31 7.0 0.72 18.8 3.86 0.1 4.04 0.1 4.18 0.1 5.03 0.0 4.68 0.0 --- --- --- ---
Methanol 1.09 10.3 0.00 64.9 1.30 7.2 0.78 17.4 3.87 0.1 4.04 0.1 4.21 0.1 5.03 0.0 4.77 0.0 --- --- --- ---
Water 1.13 9.4 0.00 63.2 1.32 6.8 0.67 20.4 3.86 0.1 4.04 0.1 4.15 0.1 5.03 0.0 4.59 0.0 --- --- --- ---
3a 3b 3c 3d 3e 3f 3g
Isolated 1.86 4.2 0.00 95.8 4.42 0.1 5.78 0.0 5.60 0.0 6.66 0.0 6.85 0.0 --- --- --- --- --- --- --- ---
CH2Cl2 1.83 4.3 0.00 93.9 2.58 1.2 3.34 0.3 4.27 0.1 5.27 0.0 3.57 0.2 --- --- --- --- --- --- --- ---
Acetone 1.74 4.8 0.00 91.8 2.29 1.9 2.92 0.7 4.07 0.1 5.07 0.0 2.89 0.7 --- --- --- --- --- --- --- ---
3 Acetonitrile 1.71 5.1 0.00 90.6 2.18 2.3 2.76 0.9 3.99 0.1 4.99 0.0 2.63 1.1 --- --- --- --- --- --- --- ---
DMSO 1.69 5.2 0.00 90.1 2.14 2.4 2.71 0.9 3.97 0.1 4.96 0.0 2.54 1.2 --- --- --- --- --- --- --- ---
Methanol 1.71 5.0 0.00 90.8 2.19 2.2 2.78 0.8 4.00 0.1 5.00 0.0 2.66 1.0 --- --- --- --- --- --- --- ---
Water 1.68 5.3 0.00 89.5 2.10 2.6 2.64 1.0 3.94 0.1 4.93 0.0 2.43 1.5 --- --- --- --- --- --- --- ---
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Table S3: Compounds 1, 2 and 3 relative enthalpy energies (ΔH) in kcal mol-1 and corresponding populations (%P) obtained at the B3LYP-D3/aug-cc-pVDZ levelfor the isolated compounds and by using the IEF-PCM implicit solvent model with dichloromethane, acetone, acetonitrile, DMSO, methanol and water dielectricconstants.
1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
ΔH %P ΔH %P ΔH %P ΔH %P ΔH %P ΔH %P ΔH %P ΔH %P ΔH %P ΔH %P ΔH %P
Isolated 0.00 61.1 0.31 36.4 2.21 1.5 2.57 0.8 3.45 0.2 4.39 0.0 4.47 0.0 6.19 0.0 6.39 0.0 8.03 0.0 8.22 0.0
CH2Cl2 0.00 46.1 0.31 27.3 1.52 3.6 0.51 19.6 1.81 2.2 4.27 0.0 2.25 1.0 3.38 0.2 3.90 0.1 4.93 0.0 6.35 0.0
Acetone 0.00 36.5 0.23 24.8 1.46 3.1 0.08 31.9 1.59 2.5 2.88 0.3 2.49 0.5 2.92 0.3 3.58 0.1 4.47 0.0 6.11 0.0
1 Acetonitrile 0.09 32.4 0.29 23.1 1.53 2.9 0.00 37.7 1.60 2.5 2.86 0.3 2.45 0.6 2.84 0.3 3.56 0.1 4.39 0.0 6.11 0.0
DMSO 0.14 31.2 0.33 22.6 1.57 2.8 0.00 39.5 1.64 2.5 2.87 0.3 2.45 0.6 2.83 0.3 3.57 0.1 4.39 0.0 6.13 0.0
Methanol 0.07 33.0 0.27 23.4 1.51 2.9 0.00 36.9 1.59 2.5 2.85 0.3 2.44 0.6 2.84 0.3 3.55 0.1 4.39 0.0 6.10 0.0
Water 0.23 29.2 0.41 21.5 1.65 2.6 0.00 42.7 1.68 2.5 2.90 0.3 2.48 0.6 2.84 0.4 3.61 0.1 4.40 0.0 6.18 0.0
2a 2b 2c 2d 2e 2f 2g 2h 2i
Isolated 0.97 15.8 0.00 81.1 1.95 3.03 --- --- 4.10 0.1 5.02 0.0 5.94 0.0 5.98 0.0 8.58 0.0 --- --- --- ---
CH2Cl2 1.29 8.4 0.00 74.5 1.23 9.3 1.35 7.6 3.87 0.1 4.45 0.0 4.62 0.0 4.45 0.0 5.69 0.0 --- --- --- ---
Acetone 1.40 6.8 0.00 72.2 1.28 8.3 1.04 12.5 3.84 0.1 4.46 0.0 4.48 0.0 5.06 0.0 5.21 0.0 --- --- --- ---
2 Acetonitrile 1.43 6.4 0.00 70.7 1.29 8.0 0.93 14.8 3.82 0.1 4.45 0.0 4.44 0.0 5.06 0.0 5.02 0.0 --- --- --- ---
DMSO 1.43 6.2 0.00 70.2 1.29 7.9 0.89 15.5 3.81 0.1 4.45 0.0 4.43 0.0 5.06 0.0 4.97 0.0 --- --- --- ---
Methanol 1.42 6.4 0.00 70.9 1.29 8.0 0.94 14.5 3.82 0.1 4.46 0.0 4.45 0.0 5.06 0.0 5.04 0.0 --- --- --- ---
Water 1.45 6.0 0.00 69.4 1.30 7.8 0.85 16.5 3.80 0.1 4.44 0.0 4.41 0.0 5.06 0.0 4.91 0.0 --- --- --- ---
3a 3b 3c 3d 3e 3f 3g
Isolated 2.26 2.1 0.00 97.7 3.73 0.2 5.86 0.0 5.88 0.0 6.90 0.0 6.79 0.0 --- --- --- --- --- --- --- ---
CH2Cl2 2.12 2.6 0.00 93.6 1.99 3.2 3.47 0.3 4.57 0.0 5.52 0.0 3.66 0.2 --- --- --- --- --- --- --- ---
Acetone 2.03 3.0 0.00 91.0 1.72 5.0 3.07 0.5 4.38 0.1 5.39 0.0 3.08 0.5 --- --- --- --- --- --- --- ---
3 Acetonitrile 1.98 3.1 0.00 89.6 1.62 5.8 2.92 0.6 4.31 0.1 5.32 0.0 2.85 0.7 --- --- --- --- --- --- --- ---
DMSO 1.97 3.2 0.00 89.1 1.58 6.1 2.87 0.7 4.29 0.1 5.30 0.0 2.76 0.8 --- --- --- --- --- --- --- ---
Methanol 1.99 3.1 0.00 89.8 1.63 5.7 2.94 0.6 4.32 0.1 5.33 0.0 2.88 0.7 --- --- --- --- --- --- --- ---
Water 1.95 3.3 0.00 88.3 1.54 6.6 2.81 0.8 4.25 0.1 5.27 0.0 2.66 1.0 --- --- --- --- --- --- --- ---
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Table S4: Compounds 1, 2 and 3 relative Gibbs free energies (ΔG) in kcal mol-1 and corresponding populations (%P) obtained at the B3LYP-D3/aug-cc-pVDZlevel for the isolated compounds and by using the IEF-PCM implicit solvent model with dichloromethane, acetone, acetonitrile, DMSO, methanol and waterdielectric constants.
1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
ΔG %P ΔG %P ΔG %P ΔG %P ΔG %P ΔG %P ΔG %P ΔG %P ΔG %P ΔG %P ΔG %P
Isolated 0.51 24.0 0.77 15.4 1.64 3.5 0.00 56.5 2.97 0.4 5.32 0.0 4.05 0.1 4.26 0.0 4.91 0.0 6.51 0.0 7.76 0.0
CH2Cl2 1.08 11.0 0.00 68.8 2.30 1.4 0.79 18.0 2.88 0.5 5.04 0.0 3.63 0.1 4.17 0.1 4.58 0.0 6.41 0.0 8.14 0.0
Acetone 1.11 8.9 0.00 58.1 2.14 1.6 0.41 29.0 2.57 0.8 3.34 0.2 2.25 1.3 3.75 0.1 4.32 0.0 5.86 0.0 7.77 0.0
1 Acetonitrile 1.13 7.3 0.00 49.4 2.06 1.5 0.13 39.9 2.46 0.8 3.32 0.2 2.51 0.7 3.56 0.1 4.23 0.0 5.65 0.0 7.61 0.0
DMSO 1.16 7.2 0.00 51.5 2.07 1.6 0.18 37.9 2.46 0.8 3.35 0.2 2.58 0.7 3.52 0.1 4.22 0.0 5.60 0.0 7.59 0.0
Methanol 1.13 7.6 0.00 50.9 2.07 1.5 0.17 38.1 2.48 0.8 3.34 0.2 2.49 0.8 3.58 0.1 4.24 0.0 5.68 0.0 7.64 0.0
Water 1.35 5.6 0.22 37.6 2.20 1.3 0.00 54.1 2.62 0.6 3.49 0.1 2.80 0.5 3.60 0.1 4.35 0.0 5.68 0.0 7.68 0.0
2a 2b 2c 2d 2e 2f 2g 2h 2i
Isolated 0.46 27.0 0.00 58.9 0.85 14.0 --- --- 4.64 0.0 4.97 0.0 5.52 0.0 3.92 0.1 8.04 0.0 --- --- --- ---
CH2Cl2 2.03 2.7 0.00 82.4 1.72 4.5 1.23 10.3 3.58 0.2 5.50 0.0 5.37 0.0 6.52 0.0 6.89 0.0 --- --- --- ---
Acetone 2.28 1.7 0.00 80.8 1.96 2.9 1.02 14.4 3.79 0.1 5.92 0.0 5.54 0.0 5.08 0.0 6.52 0.0 --- --- --- ---
2 Acetonitrile 2.43 1.4 0.00 84.6 2.00 2.9 1.21 11.0 3.92 0.1 6.03 0.0 5.62 0.0 5.33 0.0 5.74 0.0 --- --- --- ---
DMSO 2.44 1.4 0.00 84.8 1.97 3.0 1.23 10.7 3.92 0.1 6.01 0.0 5.63 0.0 5.35 0.0 6.05 0.0 --- --- --- ---
Methanol 2.43 1.4 0.00 84.5 2.02 2.8 1.20 11.2 3.92 0.1 6.04 0.0 5.62 0.0 5.32 0.0 5.44 0.0 --- --- --- ---
Water 2.44 1.4 0.00 84.7 1.91 3.3 1.24 10.5 3.92 0.1 6.00 0.0 5.62 0.0 5.38 0.0 6.24 0.0 --- --- --- ---
3a 3b 3c 3d 3e 3f 3g
Isolated 2.92 0.7 0.00 99.3 5.80 0.0 6.94 0.0 7.35 0.0 7.72 0.0 7.12 0.0 --- --- --- --- --- --- --- ---
CH2Cl2 2.93 0.7 0.00 98.9 3.72 0.2 4.15 0.1 5.52 0.0 4.71 0.0 4.25 0.1 --- --- --- --- --- --- --- ---
Acetone 2.90 0.7 0.00 98.7 3.54 0.2 3.69 0.2 5.42 0.0 6.33 0.0 4.07 0.1 --- --- --- --- --- --- --- ---
3 Acetonitrile 2.85 0.8 0.00 98.5 3.48 0.3 3.59 0.2 5.30 0.0 6.31 0.0 3.88 0.1 --- --- --- --- --- --- --- ---
DMSO 2.82 0.8 0.00 98.4 3.44 0.3 3.55 0.2 5.24 0.0 6.30 0.0 3.81 0.2 --- --- --- --- --- --- --- ---
Methanol 2.86 0.8 0.00 98.6 3.49 0.3 3.61 0.2 5.33 0.0 6.31 0.0 3.92 0.1 --- --- --- --- --- --- --- ---
Water 2.76 0.9 0.00 98.3 3.39 0.3 3.47 0.3 5.18 0.0 6.27 0.0 3.69 0.2 --- --- --- --- --- --- --- ---
S8
a)
1a 1b 1d0
50
100
Inte
nsit
y(k
mm
ol-1
)
Conformer
Amide A (CH2Cl
2)
Amide A (CH3CN)
b)
2a 2b 2d0
50
100
150
Amide A (CH2Cl
2)
Amide A (CH3CN)
Inte
ns
ity
(km
mo
l-1)
Conformer
c)
0
20
40
60
80
100
120
140
160
180
Conformer3d3c3b
Inte
nsit
y(k
mm
ol-1
)
3a
Amide A (CH2Cl2)
Amide A (CH3CN)
Figure S3: Ac-Gly-NHMe calculated (B3LYP-D3/aug-cc-pVDZ) IR intensities for a) Amide A and Amide B absorptions for conformers 1a, 1b and 1d inCH2Cl2 and acetonitrile. b) Amide A and Amide B absorptions for conformers 2a, 2b and 2d in CH2Cl2 and acetonitrile and c). Amide A and Amide Babsorptions for conformers 3a, 3b and 3d in CH2Cl2 and acetonitrile
S9
Ac-Gly-NHMe1a 1b 1d
ρ = 0.022 au2ρ = +0.066 auε = 0.034 au
CF3-C(O)-Gly-NHMe2a 2b 2c 2d
ρ = 0.0172ρ = +0.052ε = 0.029 au
Figure S4: QTAIM molecular graphs of compounds 1 and 2 most stable conformers obtained from B3LYP-D3/aug-cc-pVDZ optimisations. Electron density (ρ), Laplacian of the electron density (2ρ) and ellipticity values (ε, au) in the intramolecular hydrogen bond bond critical point (BCP) are indicated for each case.Green points represent BCPs and red points represent ring critical points (RCPs).
S10
Ac-Gly-NHMe1a 1b 1d
0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
1.0
-0.075
C(O)V(N, H)
V(O)
C(N)
EL
F
N-H...O bond path
+0.087
0 1 2 3 4 5 6
0.0
0.2
0.4
0.6
0.8
1.0C(O)V(N, H)
V(O)
C(N)
EL
FN-H...O bond path
-0.054+0.0860 1 2 3 4 5 6
0.0
0.2
0.4
0.6
0.8
1.0C(O)V(N, H)
V(O)
C(N)
EL
F
N-H...N bond path
-0.042+0.085
CVBI = +0.012 CVBI = +0.032 CVBI = +0.042CF3-C(O)-Gly-NHMe
2a 2b 2c 2d
0 1 2 3 4 5 6
0.0
0.2
0.4
0.6
0.8
1.0
-0.058
C(O)V(N, H)
V(O)
C(N)
ELF
N-H...O bond path
+0.086
0 1 2 3 4 5 6
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
C(O)
V(O)
V(N, H)C(N)
+0.088 -0.058
N-H...O bond path
EL
F
0 1 2 3 4 5 6
0.0
0.2
0.4
0.6
0.8
1.0C(O)V(N, H)
V(O)
C(N)
EL
FN-H...N bond path
+0.060+0.0850 1 2 3 4 5 6
0.0
0.2
0.4
0.6
0.8
1.0 C(O)V(N, H)
V(O)
C(N)
EL
F
N-H...N bond path
+0.041+0.086
CVBI = +0.027 CVBI = +0.030 CVBI = +0.030 CVBI = +0.045Figure S5: ELF localization domains (0.8 au isodensity value) of compounds 1 and 2 main conformers obtained from B3LYP-D3/aug-cc-pVDZ optimisations.Graphs of ELF value along the bond path of the IHB are given for each case. Core valence bifurcation index (CVBI) values (au) for each case obtained fromthose graphs are also indicated.
S11
Ac-Gly-NHMe1a 1b 1d
sign(2) = -0.022 sign(2) = -0.019 sign(2) = -0.016CF3-C(O)-Gly-NHMe
2a 2b 2c 2d
sign(2) = -0.017 sign(2) = -0.020 sign(2) = -0.020 sign(2) = -0.015Figure S6: NCI isosurface plots of compounds 1 and 2 main conformers obtained from B3LYP-D3/aug-cc-pVDZ optimisations. The figures were obtainedwith a reduced density gradient (RDG) value of 0.6 and the blue-green-red values ranging from -0.02 to 0.02 au. Graph of the RDG vs sign(2) are given foreach case. Values of sign(2) (au) corresponding to IHBs peaks in the (RDG) vs sign(2) graphs are given for each case.
S12
Ac-Gly-NHMe1a 1b 1d
sign(2) = -0.022 sign(2) = -0.019 sign(2) = -0.015CF3-C(O)-Gly-NHMe
2a 2b 2c 2d
sign(2) = sign(2) = -0.020 sign(2) = -0.020 sign(2) = -0.015Figure S7: DORI isosurface plots of compounds 1 and 2 main conformers obtained from B3LYP-D3/aug-cc-pVDZ optimisations. The figures were obtainedwith a DORI value of 0.9 au and the blue-green-red values ranging from -0.02 to 0.02 au. Values of sign(2) (au) corresponding to IHBs peaks in the DORI vssign(2) graphs are given for each case.
S13
Ac-Gly-NHMe1a 1b 1d
nO(1) *NH = 2.57 nO(1) *NH = 0.67 nN *NH = 1.24
nO(2) *NH = 3.76 nO(2) *NH = 2.04CF3-C(O)-Gly-NHMe
2a 2b 2c 2d
nO(1) *NH = 1.69 nO(1) *NH = 0.79 nO(1) *NH = 0.83 nN *NH = 1.24
nO(2) *NH = 2.65 nO(2) *NH = 2.49 nO(2) *NH = 2.59 nF(2) *NH = 1.10
nF(2) *NH = 1.10 nF(2) *NH = 0.94 nF(2) *NH = 0.94Figure S8: NBO plots of n *NH interactions for main conformers of 1 and 2. Figures were obtained at the B3LYP-D3/aug-cc-pVDZ level with an isovalue of 0.04 au. n *NH energy values are given in kcal mol-1.
S14
Table S5: Compounds 1, 2 and 3 3JHH calculated SSCCs (in Hz) at the BHandH/EPR-III and SOPPA(CCSD)/EPR-III on B3LYP-D3/aug-cc-pVDZ optimisedgeometries for the isolated compounds.
1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
3JH10H13 (BHand/EPR-III) 7.01 2.76 3.07 9.73 7.82 3.81 3.12 11.35 3.54 10.56 8.37
3JH11H13 (BHand/EPR-III) 6.47 2.79 2.71 4.61 7.71 10.23 3.12 5.22 3.00 5.72 8.17
1 (3JH10H11 + 3JH11H13)/2 6.74 2.78 2.89 7.17 7.77 7.02 3.12 8.29 3.27 8.14 8.27
3JH10H13 [SOPPA(CCSD)/EPR-III] 6.01 1.76 2.04 8.33 6.64 3.22 2.16 10.04 2.55 9.42 7.63
3JH11H13 [SOPPA(CCSD)/EPR-III] 5.66 1.78 1.72 4.00 7.02 8.73 2.16 4.53 2.04 5.10 6.95
(3JH10H11 + 3JH11H13)/2 5.84 1.77 1.88 6.17 6.83 5.98 2.16 7.29 2.30 7.26 7.29
2a 2b 2c 2d 2e 2f 2g 2h 2i
3JH14H15 (BHand/EPR-III) 8.15 3.01 2.57 6.65 2.60 2.30 5.40 2.80 8.45 --- ---
3JH15H16 (BHand/EPR-III) 6.62 2.57 3.24 8.07 2.59 12.08 9.74 2.75 3.90 --- ---
2 (3JH14H15 + 3JH15H16)/2 7.39 2.79 2.91 7.36 2.60 7.19 7.57 2.78 6.18 --- ---
3JH14H15 [SOPPA(CCSD)/EPR-III] 6.65 2.43 2.00 5.86 2.62 1.95 5.38 2.76 7.58 --- ---
3JH15H16 [SOPPA(CCSD)/EPR-III] 5.83 1.99 2.64 6.58 2.60 10.07 9.97 2.72 3.11 --- ---
(3JH14H15 + 3JH15H16)/2 6.24 2.21 2.32 6.22 2.61 6.01 7.68 2.74 5.35
3a 3b 3c 3d 3e 3f 3g
3JH3H6 (BHand/EPR-III) 3.28 2.57 2.98 10.29 8.96 0.03 1.39 --- --- ---
3JH4H6 (BHand/EPR-III) 10.25 2.66 2.98 5.77 7.69 11.80 7.87 --- --- ---
3 (3JH3H6 + 3JH4H6)/2 6.77 2.62 2.98 8.03 8.33 5.92 4.63 --- --- ---
3JH3H6 [SOPPA(CCSD)/EPR-III] 2.70 1.84 2.28 9.40 7.92 -0.41 0.81 --- --- ---
3JH4H6 [SOPPA(CCSD)/EPR-III] 8.98 1.92 2.28 5.09 6.88 10.61 7.13 --- --- ---
(3JH3H6 + 3JH4H6)/2 5.84 1.88 2.28 7.25 7.40 5.10 3.97 --- --- ---
S15
a)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
E(
i
) x
(3J
H1
0H
11
+3
JH
11
H13)/
2]
H2OCH
3OHDMSOCH
3CNAcetoneCH
2Cl
2
ExperimentalBHandHSOPPA(CCSD)
b)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
H(
i
) x
(3J
H1
0H
11
+3J
H11H
13)/
2]
H2OCH
3OHDMSOCH
3CNAcetoneCH
2Cl
2
ExperimentalBHandHSOPPA(CCSD)
c)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
G(
i
) x
(3J
H1
0H
11
+3J
H11
H1
3)/
2]
H2OCH
3OHDMSOCH
3CNAcetoneCH
2Cl
2
ExperimentalBHandHSOPPA(CCSD)
d)
0
1
2
3
4
5
6
I
R(
i
) x
(3J
Ha
Hb)/
2]
IR(CH
2Cl
2)
IR Corr.(CH
2Cl
2)
ExperimentalIR (BHandH)
Figure S9: Sum of all Ac-Gly-NHMe conformers contributions [( � i/ � T) x J] for the 3JH10H11 and 3JH11H13 SSCCs average values (3JH10H11 + 3JH11H13/2) obtainedin different solvents (B3LYP-D3/aug-cc-pVDZ level) by using the IEF-PCM model. Conformer contributions ( � i/ � T) values to 3JHH from a) ΔE; b) ΔH; c)ΔG; d) Experimental IR (using BHandH calculated 3JHH) uncorrected and corrected (IR Corr.) by conformers calculated infrared intensities.
S16
a)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
E(
i
) x
(3J
H1
4H
15
+3
JH
15
H1
6)/
2]
H2OCH
3OHDMSOCH
3CNAcetoneCH
2Cl
2
ExperimentalBHandHSOPPA(CCSD)
b)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
H(
i
) x
(3J
H14H
15
+3J
H1
5H
16)/
2]
H2OCH
3OHDMSOCH
3CNAcetoneCH
2Cl
2
ExperimentalBHandHSOPPA(CCSD)
c)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
G(
i
) x
(3J
H14H
15
+3J
H1
5H
16)/
2]
H2OCH
3OHDMSOCH
3CNAcetoneCH
2Cl
2
ExperimentalBHandHSOPPA(CCSD)
d)
0
1
2
3
4
5
I
R(
i
) x
(3J
HaH
b)/
2]
IR(CH
3CN)
IR(CH
2Cl
2)
IR Corr.(CH
2Cl
2)
IR Corr.(CH
3CN)
ExperimentalIR (BHandH)
Figure S10: Sum of all CF3-C(O)-Gly-NHMe conformers contributions [( � i/ � T) x J] for the 3JH14H15 and 3JH15H16 SSCCs average values (3JH14H15 + 3JH15H16)/2obtained in different solvents (B3LYP-D3/aug-cc-pVDZ level) by using the IEF-PCM model. Conformer contributions ( � i/ � T) values to 3JHH from a) ΔE; b)ΔH; c) ΔG; d) Experimental IR (using BHandH calculated 3JHH) and corrected IR (IR Corr.) with calculated infrared intensities.
S17
a)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
E(
i
) x
(3J
H3
H6
+3
JH
4H
6)/
2]
H2OCH
3OHDMSOCH
3CNAcetoneCH
2Cl
2
ExperimentalBHandHSOPPA(CCSD)
b)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
H(
i
) x
(3J
H3
H6
+3
JH
4H
6)/
2]
H2OCH
3OHDMSOCH
3CNAcetoneCH
2Cl
2
ExperimentalBHandHSOPPA(CCSD)
c)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
G(
i
) x
(3J
H3H
6+
3J
H4H
6)/
2]
H2OCH
3OHDMSOCH
3CNAcetoneCH
2Cl
2
ExperimentalBHandHSOPPA(CCSD)
Figure S11: Sum of all Ac-Gly-N(Me)2 conformers contributions [( � i/ � T) x J] for the 3JH3H6 and 3JH4H6 SSCCs average values (3JH3H6 + 3JH4H6)/2 obtained indifferent solvents (B3LYP-D3/aug-cc-pVDZ level) by using the IEF-PCM model. Conformer contributions ( � i/ � T) values to 3JHH from a) ΔE; b) ΔH and c)ΔG
S18
1H NMR Spectra (Bruker avance III 600 MHz)1. Ac-Gly-NHMe
Spectrum S1: Ac-Gly-NHMe 1H NMR Spectrum in CD2Cl2.
10 9 8 7 6 5 4 3 2 1 0 ppm
3.0
8
3.0
0
2.0
7
0.8
9
0.9
0
NAME Ac-gly-nhmeEXPNO 1PROCNO 1Date_ 20140729Time 10.41INSTRUM spectPROBHD 5 mm PATXI 1H/PULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 6602.113 HzFIDRES 0.100740 HzAQ 4.9633098 secRG 32DW 75.733 usecDE 6.50 usecTE -0.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 600.1727043 MHzNUC1 1HP1 7.50 usecSI 131072SF 600.1700242 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
3.84 ppm
3.825
3.834
2.78 ppm
2.777
2.785
6.0 ppm
5.923
6.184
1.995 ppm
1.993
S19
Spectrum S2: Ac-Gly-NHMe 1H NMR Spectrum in acetone-d6.
10 9 8 7 6 5 4 3 2 1 0 ppm
3.0
0
3.2
6
2.1
1
0.8
90
.95
NAME gly-dip-acetonaEXPNO 1PROCNO 1Date_ 20120124Time 11.34INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 32768SOLVENT AcetoneNS 4DS 0SWH 12335.526 HzFIDRES 0.376450 HzAQ 1.3282462 secRG 203DW 40.533 usecDE 6.50 usecTE 298.1 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 15.00 usecSI 131072SF 600.1700080 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
7.27.4 ppm
7.153
7.343
3.77 ppm
3.762
3.772
2.69 ppm
2.684
2.692
1.925 ppm
1.925
S20
Spectrum S3: Ac-Gly-NHMe 1H NMR Spectrum in CD3CN.
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
3.0
3
3.0
2
2.0
3
0.9
6
1.0
0
NAME gli-dip-CN-nhEXPNO 2PROCNO 1Date_ 20120404Time 16.48INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zg30TD 65536SOLVENT CD3CNNS 4DS 0SWH 6009.615 HzFIDRES 0.091699 HzAQ 5.4526453 secRG 144DW 83.200 usecDE 6.50 usecTE 298.1 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 9.63 usecSI 131072SF 600.1700174 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
3.68 ppm
3.675
3.685
2.66 ppm
2.657
2.665
6.66.8 ppm
6.526
6.715
1.92 ppm
1.917
S21
Spectrum S4: Ac-Gly-NHMe 1H NMR Spectrum in DMSO-d6.
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
2.7
6
2.9
5
2.0
0
0.9
5
0.9
7
NAME gly-dip-dmsoEXPNO 1PROCNO 1Date_ 20120201Time 17.19INSTRUM spectPROBHD 5 mm PATBO BB-PULPROG zg30TD 65536SOLVENT DMSONS 8DS 0SWH 6602.113 HzFIDRES 0.100740 HzAQ 4.9633098 secRG 203DW 75.733 usecDE 6.50 usecTE 297.7 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 21.50 usecSI 131072SF 600.1700053 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
8.10 ppm
8.081
7.75 ppm
7.737
7.741
ppm3.601
3.611
ppm
1.847
ppm
2.569
2.577
S22
Spectrum S5: Ac-Gly-NHMe 1H NMR Spectrum in CD3OH.
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
2.6
1
2.6
6
1.8
0
0.8
4
0.8
5
NAME gli-dip-cd3oh-nhEXPNO 1PROCNO 1Date_ 20120701Time 10.06INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zg30TD 65536SOLVENT MeODNS 8DS 0SWH 6602.113 HzFIDRES 0.100740 HzAQ 4.9633098 secRG 5.6DW 75.733 usecDE 6.50 usecTE 298.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.15 usecSI 131072SF 600.1700093 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
3.793.80 ppm
3.791
3.801
2.74 ppm
2.732
2.740
8.0 ppm
7.894
8.249
2.00 ppm
2.002
S23
Spectrum S6: Ac-Gly-NHMe 1H NMR Spectrum in H2O. WATERGATE solvent suppression was used.
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
2.8
7
3.0
0
2.2
3
0.6
3
0.7
6
NAME glidip_h2o_d2oEXPNO 4PROCNO 1Date_ 20121113Time 21.25INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG p3919gpTD 65536SOLVENT H2O+D2ONS 256DS 0SWH 6613.757 HzFIDRES 0.100918 HzAQ 4.9545717 secRG 203DW 75.600 usecDE 6.50 usecTE 298.8 KD1 1.00000000 secD16 0.00020000 secD19 0.00016667 secTD0 1
======== CHANNEL f1 ========NUC1 1HP0 7.15 usecP1 7.15 usecP27 7.15 usecSI 32768SF 600.1698238 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
2.052.06 ppm
2.051
2.74 ppm
2.733
2.741
3.85 ppm
3.849
3.859
8.0 ppm
7.855
8.297
S24
2. CF3-C(O)-Gly-NHMe
Spectrum S7: CF3-C(O)-Gly-NHMe 1H NMR Spectrum in CD2Cl2.
9 8 7 6 5 4 3 2 1 0 ppm
3.0
0
2.0
1
1.0
7
0.9
2
NAME CF3-gly-nhmeEXPNO 1PROCNO 1Date_ 20140729Time 10.56INSTRUM spectPROBHD 5 mm PATXI 1H/PULPROG zg30TD 65536SOLVENT CD2Cl2NS 64DS 0SWH 6613.757 HzFIDRES 0.100918 HzAQ 4.9545717 secRG 203DW 75.600 usecDE 6.50 usecTE -0.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 600.1726892 MHzNUC1 1HP1 7.50 usecSI 131072SF 600.1700255 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
5.65.7 ppm
5.618
3.96 ppm
3.955
3.963
7.2 ppm
7.194
2.86 ppm
2.842
2.850
S25
Spectrum S8: CF3-C(O)-Gly-NHMe 1H NMR Spectrum in acetone-d6.
9 8 7 6 5 4 3 2 1 0 ppm
3.1
2
2.2
0
0.9
1
0.8
2
NAME cf3gli_dip_nh_acetonaEXPNO 1PROCNO 1Date_ 20120731Time 10.42INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zg30TD 65536SOLVENT AcetoneNS 8DS 0SWH 6602.113 HzFIDRES 0.100740 HzAQ 4.9633098 secRG 101DW 75.733 usecDE 6.50 usecTE 298.1 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.15 usecSI 131072SF 600.1700090 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
3.963.97 ppm
3.962
3.971
2.74 ppm
2.726
2.734
8 ppm
7.306
8.528
S26
Spectrum S9: CF3-C(O)-Gly-NHMe 1H NMR Spectrum in CD3CN.
9 8 7 6 5 4 3 2 1 0 ppm
3.0
0
2.0
2
0.8
9
0.8
4
NAME CF3-gli-CD3CNEXPNO 1PROCNO 1Date_ 20121106Time 19.24INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zg30TD 65536SOLVENT CD3CNNS 32DS 0SWH 6613.757 HzFIDRES 0.100918 HzAQ 4.9545717 secRG 203DW 75.600 usecDE 10.00 usecTE 298.4 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.15 usecSI 131072SF 600.1700182 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
3.84 ppm
3.836
3.844
2.70 ppm
2.690
2.698
7.07.58.0 ppm
6.503
7.757
S27
Spectrum S10: CF3-C(O)-Gly-NHMe 1H NMR Spectrum in DMSO-d6.
11 10 9 8 7 6 5 4 3 2 1 0 ppm
2.8
8
2.0
0
0.9
9
1.0
0
NAME CF3-gli-DMSOEXPNO 1PROCNO 1Date_ 20121106Time 15.56INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zg30TD 65536SOLVENT DMSONS 128DS 0SWH 7911.393 HzFIDRES 0.120718 HzAQ 4.1419253 secRG 161DW 63.200 usecDE 10.00 usecTE 298.4 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.15 usecSI 131072SF 600.1700051 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
3.763.78 ppm
3.757
3.767
2.60 ppm
2.597
2.605
9 ppm
7.976
7.980
9.625
S28
Spectrum S11: CF3-C(O)-Gly-NHMe 1H NMR Spectrum in CD3OH. Solvent presaturation experiment was used.
10 9 8 7 6 5 4 3 2 1 ppm
2.8
4
2.0
0
0.5
9
NAME CF3-gli-CD3OHEXPNO 2PROCNO 1Date_ 20121106Time 10.09INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zgprTD 32768SOLVENT MeODNS 64DS 0SWH 7183.908 HzFIDRES 0.219235 HzAQ 2.2807028 secRG 80.6DW 69.600 usecDE 10.00 usecTE 298.4 KD1 1.00000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.15 usecSI 32768SF 600.1700090 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
3.92 ppm3.908
2.75 ppm
2.746
2.754
8.1 ppm
8.035
S29
Spectrum S12: CF3-C(O)-Gly-NHMe 1H NMR Spectrum in H2O. Solvent presaturation experiment was used.
10 9 8 7 6 5 4 3 2 1 0 ppm
2.8
4
2.0
0
0.5
9
NAME CF3-gli-CD3OHEXPNO 2PROCNO 1Date_ 20121106Time 10.09INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zgprTD 32768SOLVENT MeODNS 64DS 0SWH 7183.908 HzFIDRES 0.219235 HzAQ 2.2807028 secRG 80.6DW 69.600 usecDE 10.00 usecTE 298.4 KD1 1.00000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.15 usecSI 32768SF 600.1700090 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
3.92 ppm3.908
2.75 ppm
2.746
2.754
8.1 ppm
8.035
S30
O
N
N
OH
3. Ac-Gly-N(Me)2
Spectrum S13: Ac-Gly-N(Me)21H NMR Spectrum in CD2Cl2.
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
3.0
0
2.9
52.9
7
2.0
5
0.9
1
NAME N-dir_metil_GLI_CD2Cl2EXPNO 1PROCNO 1Date_ 20121219Time 9.59INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zg30TD 65536SOLVENT CD2Cl2NS 32DS 0SWH 6602.113 HzFIDRES 0.100740 HzAQ 4.9633098 secRG 32DW 75.733 usecDE 6.50 usecTE 298.8 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.15 usecSI 65536SF 600.1690124 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
4.00 ppm3.999
4.007
2.95 ppm
2.943
2.964
6.8 ppm
6.813
1.99 ppm
1.987
S31
O
N
N
OH
Spectrum S14: Ac-Gly-N(Me)21H NMR Spectrum in acetone-d6.
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
2.7
3
3.0
03.0
4
2.0
4
0.8
0
NAME N-dir_metil_GLI_acetonaEXPNO 1PROCNO 1Date_ 20121218Time 18.24INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zg30TD 65536SOLVENT AcetoneNS 32DS 0SWH 6613.757 HzFIDRES 0.100918 HzAQ 4.9545717 secRG 22.6DW 75.600 usecDE 6.50 usecTE 298.8 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.15 usecSI 65536SF 600.1689977 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
3.98 ppm3.973
3.981
3.0 ppm
2.895
3.007
7.2 ppm
7.187
1.94 ppm
1.935
S32
O
N
N
OH
Spectrum S15: Ac-Gly-N(Me)21H NMR Spectrum in CD3CN.
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
3.0
0
3.1
73
.20
2.1
3
0.9
1
NAME N-dir_metil_GLI_CD3CNEXPNO 1PROCNO 1Date_ 20121218Time 17.15INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zg30TD 65536SOLVENT CD3CNNS 32DS 0SWH 6602.113 HzFIDRES 0.100740 HzAQ 4.9633098 secRG 50.8DW 75.733 usecDE 6.50 usecTE 298.8 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.15 usecSI 131072SF 600.1700167 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
3.93 ppm3.924
3.932
2.9 ppm
2.878
2.928
6.76.8 ppm
6.747
1.92 ppm
1.917
S33
O
N
N
OH
Spectrum S16: Ac-Gly-N(Me)21H NMR Spectrum in DMSO-d6.
10 9 8 7 6 5 4 3 2 1 0 ppm
2.8
8
3.0
03.0
9
1.9
3
0.8
3
NAME N-dir_metil_GLI_DMSOEXPNO 1PROCNO 1Date_ 20121218Time 15.50INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zg30TD 65536SOLVENT DMSONS 32DS 0SWH 6602.113 HzFIDRES 0.100740 HzAQ 4.9633098 secRG 32DW 75.733 usecDE 6.50 usecTE 298.8 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.15 usecSI 131072SF 600.1700000 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
3.90 ppm3.883
3.892
2.9 ppm
2.823
2.937
7.90 ppm
7.912
1.86 ppm
1.859
S34
O
N
N
OH
Spectrum S17: Ac-Gly-N(Me)21H NMR Spectrum in CD3OH.
9 8 7 6 5 4 3 2 1 0 ppm
5.6
2
5.6
35
.63
3.6
0
1.4
5
NAME N-dir_metil_GLI_CD3OHEXPNO 1PROCNO 1Date_ 20121218Time 19.55INSTRUM spectPROBHD 5 mm TBI 1H/13PULPROG zg30TD 65536SOLVENT MeODNS 256DS 0SWH 6578.947 HzFIDRES 0.100387 HzAQ 4.9807858 secRG 4DW 76.000 usecDE 6.50 usecTE 298.8 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 10.00 usecSI 65536SF 600.1700000 MHzWDW EMSSB 0LB 0.00 HzGB 0PC 1.00
4.06 ppm4.050
4.058
3.0 ppm
2.961
3.049
8.1 ppm
8.075
2.03 ppm
2.025
S35
Spectrum S18: Ac-Gly-N(Me)21H NMR Spectrum in H2O. WATERGATE solvent suppression was used.
10 9 8 7 6 5 4 3 2 1 0 ppm
2.6
0
3.0
03.1
2
1.9
3
NAME ac-gly-nme2-h2o_insercaoEXPNO 3PROCNO 1Date_ 20140807Time 12.57INSTRUM spectPROBHD 5 mm PATXI 1H/PULPROG p3919gpTD 65536SOLVENT H2O+D2ONS 256DS 2SWH 6631.300 HzFIDRES 0.101186 HzAQ 4.9414644 secRG 203DW 75.400 usecDE 6.50 usecTE -0.2 KD1 1.00000000 secD16 0.00020000 secD19 0.00025000 secTD0 1
======== CHANNEL f1 ========SFO1 600.1728310 MHzNUC1 1HP0 7.50 usecP1 7.50 usecP27 7.50 usecSI 32768SF 600.1699628 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
ppm
3.032
ppm
2.931
ppm
4.068
2.06 ppm
2.053
S36
Infrared spectra
Ac-Gly-NHMe N-H in CH2Cl2
a)
3500 3480 3460 3440 3420 3400 3380 3360
0.00
0.02
0.04
0.06
0.08
0.10
Ab
so
rba
nce
Wavenumber (cm-1)
b)
3500 3480 3460 3440 3420 3400
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
P(1b) = 31.9%
1b
Experimental SpectrumSum of deconvolded bandsDeconvolved 1aDeconvolved 1b
Ab
sorb
an
ce
Wavenumber (cm-1)
P(1a) = 68.1%
1a
c)
3640 3620 3600 3580 3560 3540 3520 3500 3480 3460
0
100
200
300
400
500
600
Ep
isilo
n
Wavenumber (cm-1)
Conformer 1aConformer 1bConformer 1d
P(1a) = 56.2%
P(1b) = 18.9%
P(1d) = 19.2%
d)
3640 3620 3600 3580 3560 3540 3520 3500 3480 3460
0
100
200
300
400
500
Ep
isilo
n
Wavenumber (cm-1)
Conformer 1aConformer 1bConformer 1d
P(1a) = 46.1%
P(1b) = 27.3%P(1d) = 19.6%
e)
3640 3620 3600 3580 3560 3540 3520 3500 3480 3460
0
50
100
150
200
250
300
350
400
Epis
ilon
Wavenumber (cm-1)
P(1a) = 11.0%
P(1b) = 68.8%
P(1d) = 18.0%
Conformer 1aConformer 1bConformer 1d
f)
3640 3620 3600 3580 3560 3540 3520 3500 3480 3460
0
100
200
300
400
500
600
700
Ep
isilo
n
Wavenumber (cm-1)
Conformer 1aConformer 1b
P(1a) = 68.1%
P(1b) = 31.9%
Figure S12: Ac-Gly-NHMe N-H stretchings region in CH2Cl2 of: a) IR experimental spectrum b)
Deconvolved experimental Spectrum. Each conformer N-H stretchings were weighted by its
B3LYP-D3/aug-cc-pVDZ populations for c) ΔE populations; d) ΔH populations and e) ΔG
populations. f) Theoretical spectrum using B3LYP-D3/aug-cc-pVDZ geometries and populations
obtained from the deconvolved experimental spectrum.
S37
a)
1750 1700 1650 1600 1550 1500 1450
0.00
0.05
0.10
0.15
0.20
0.25
0.30
b)
1720 1700 1680 1660 1640 1620 1600 1580 1560 1540 1520
0
200
400
600
800
1000
1200Conformer 1aConformer 1bConformer 1d
Ab
sorb
an
ce
Wavenumber (cm-1)
P(1a) = 56.2%
P(1d) = 19.2%
P(1b) = 18.9%
c)
1720 1700 1680 1660 1640 1620 1600 1580 1560 1540 1520
0
200
400
600
800
1000
1200
Epis
ilon
Conformer 1aConformer 1bConformer 1d
Wavenumber (cm-1)
P(1a) = 46.1%
P(1b) = 27.3%
P(1d) = 19.6%
d)
1720 1700 1680 1660 1640 1620 1600 1580 1560 1540 1520
0
200
400
600
800
1000
1200
1400
1600
1800
2000
Ep
isilo
n
Conformer 1aConformer 1bConformer 1d
Wavenumber (cm-1)
P(1a) = 11.0%
P(1d) = 18.0%
P(1b) = 68.8%
e)
1700 1680 1660 1640 1620 1600 1580 1560 1540
0
200
400
600
800
1000
1200
1400
1600
1800
Ep
isilo
n
Conformer 1aConformer 1b
P(1a) = 61.1%
P(1b) = 31.9%
Wavenumber (cm-1)
Figure S13: Ac-Gly-NHMe C=O stretchings region (~1700 cm-1; Amide I bands) and mix of
C(O)-N-H bond angle deformation/C-N bond stretching (~1550 cm-1; Amide II) in CH2Cl2 of: a)
IR experimental spectrum. Each conformer C=O bond stretchings/angular bending weighted by
its B3LYP-D3/aug-cc-pVDZ populations for b) ΔE populations; c) ΔH populations and d) ΔG
populations. e) Theoretical spectrum using B3LYP-D3/aug-cc-pVDZ geometries and populations
obtained from the deconvolved experimental spectrum.
S38
Ac-Gly-NHMe in Acetonitrile
a)
3480 3460 3440 3420 3400 3380 3360 3340 3320 3300
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14 Experimental Spectrum
Ab
sorb
an
ce
Wavenumber (cm-1)
b)
3640 3620 3600 3580 3560 3540 3520 3500 3480 3460
0
100
200
300
400
500
Ep
isilo
n
Conformer 1aConformer 1bConformer 1d
Wavenumber (cm-1)
P(1a) = 39.9%
P(1d) = 37.9%
P(1b) = 16.0%
c)
3640 3620 3600 3580 3560 3540 3520 3500 3480 3460
-50
0
50
100
150
200
250
300
350
400
Epis
ilon
Conformer 1aConformer 1bConformer 1d
Wavenumber (cm-1)
P(1a) = 32.4%
P(1b) = 23.1%
P(1d) = 37.7%
d)
3640 3620 3600 3580 3560 3540 3520 3500 3480 3460
-20
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
Ep
isilo
n
Conformer 1aConformer 1bConformer 1d
Wavenumber (cm-1)
P(1a) = 7.3%
P(1b) = 49.4%
P(1d) = 39.9%
Figure S14: Ac-Gly-NHMe N-H stretchings region (Amide A and B bands) in acetonitrile of: a)
IR experimental spectrum b) ΔE populations; c) ΔH populations and d) ΔG populations.
S39
a)
1720 1700 1680 1660 1640
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Abso
rban
ce
Wavenumber (cm-1)
b)
1710 1680 1650 1620 1590 1560 1530 1500
0
200
400
600
800
1000
1200
Conformer 1aConformer 1bConformer 1d
Ab
sorb
an
ce
Wavenumber (cm-1)
P(1a) = 39.9%
P(1b) = 16.0%
P(1d) = 37.9%
c)
1710 1680 1650 1620 1590 1560 1530 1500
0
200
400
600
800
1000
Epis
ilon
Conformer 1aConformer 1bConformer 1d
Wavenumber (cm-1)
P(1b) = 23.1%
P(1d) = 37.7%
P(1a) = 32.4%
d)
1710 1680 1650 1620 1590 1560 1530 1500
0
200
400
600
800
1000
1200
1400
1600
Ep
isilo
n
Conformer 1aConformer 1bConformer 1d
Wavenumber (cm-1)
P(1b) = 49.4%
P(1d) = 39.9%
P(1a) = 7.3%
Figure S15: Ac-Gly-NHMe C=O stretchings region (~1700 cm-1; Amide I bands) and mix of
C(O)-N-H bond angle deformation/C-N bond stretching (~1550 cm-1; Amide II) in acetonitrile of:
a) IR experimental spectrum. Each conformer bond stretchings/angular bendings were weighted
by its B3LYP-D3/aug-cc-pVDZ populations for b) ΔE populations; c) ΔH populations and d) ΔG
populations.
S40
CF3-C(O)-Gly-NHMe in CH2Cl2
a)
3500 3480 3460 3440 3420 3400 3380 3360 3340 3320 3300
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
Experimental Spectrum
Absorb
ance
Wavenumber (cm-1)
b)
3500 3480 3460 3440 3420 3400 3380 3360 3340 3320 3300
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
2b
2a
P(2b) = 59.6%
Experimental SpectrumSum of deconvolded bandsDeconvolved 2aDeconvolved 2b
P(2a) = 40.4%Ab
sorb
an
ce
Wavenumber (cm-1)
c)
3640 3620 3600 3580 3560 3540 3520 3500
0
100
200
300
400
500
600
Ep
isilo
n
P(2c) = 8.4%
Conformer 2aConformer 2bConformer 2cConformer 2d
Wavenumber (cm-1)
P(2b) = 68.0%
P(2a) = 13.7%
P(2d) = 9.6%
d)
3640 3620 3600 3580 3560 3540 3520 3500
0
100
200
300
400
500
600E
pis
ilon
Conformer 2aConformer 2bConformer 2cConformer 2d
Wavenumber (cm-1)
P(2a) = 8.4%P(2c) = 9.3%
P(2d) = 7.6%
P(2b) = 74.5%
e)
3640 3620 3600 3580 3560 3540 3520 3500
0
100
200
300
400
500
600
700
Ep
isilo
n
Conformer 2aConformer 2bConformer 2cConformer 2d
Wavenumber (cm-1)
P(2a) = 2.7% P(2c) = 4.5%P(2d) = 10.3%
P(2b) = 82.4%
f)
3640 3620 3600 3580 3560 3540 3520 3500
-100
0
100
200
300
400
500
600
700
800
Ep
isilo
n
Conformer 2aConformer 2b
P(2b) = 59.6%
P(2a) = 40.4%
Wavenumber (cm-1)
Figure S16: CF3-C(O)-Gly-NHMe N-H stretchings region (Amide A and B bands) in CH2Cl2 of:
a) IR experimental spectrum b) Deconvolved experimental Spectrum. Each conformer N-H
stretchings were weighted by its B3LYP-D3/aug-cc-pVDZ populations for c) ΔE populations; d)
ΔH populations and e) ΔG populations. f) Theoretical spectrum using B3LYP-D3/aug-cc-pVDZ
geometries and populations obtained from the deconvolved experimental spectrum.
S41
a)
1800 1750 1700 1650 1600 1550 1500
0.0
0.1
0.2
0.3
0.4
0.5
Ab
sorb
an
ce
Wavenumber (cm-1)
b)
1770 1740 1710 1680 1650 1620 1590 1560 1530
0
200
400
600
800
1000
1200
1400Conformer 2aConformer 2bConformer 2cConformer 2d
Abso
rba
nce
Wavenumber (cm-1)
P(2b) = 68.0%
P(2c) = 8.4%
P(2d) = 9.6%
P(2a) = 13.7%
c)
1770 1740 1710 1680 1650 1620 1590 1560 1530
-200
0
200
400
600
800
1000
1200
1400
1600
Ep
isilo
n
Conformer 2aConformer 2bConformer 2cConformer 2d
Wavenumber (cm-1)
P(2b) = 74.5%
P(2c) = 9.3%
P(2d) = 7.6% P(2a) = 8.4%
d)
1770 1740 1710 1680 1650 1620 1590 1560 1530
0
200
400
600
800
1000
1200
1400
1600
1800
Ep
isilo
n
Conformer 2aConformer 2bConformer 2cConformer 2d
Wavenumber (cm-1)
P(2b) = 82.4%
P(2c) = 4.5%
P(2a) = 2.7%
P(2d) = 10.3%
e)
1770 1740 1710 1680 1650 1620 1590 1560 1530 1500
0
200
400
600
800
1000
1200
1400
Ep
isilo
n
Conformer 2aConformer 2b
P(2b) = 56.6%
P(2a) = 43.4%
Wavenumber (cm-1)
Figure S17: CF3-C(O)-Gly-NHMe C=O stretchings region (~1700 cm-1; Amide I bands) and mix
of C(O)-N-H bond angle deformation/C-N bond stretching (~1550 cm-1; Amide II) in CH2Cl2 of:
a) IR experimental spectrum. Each conformer bond stretchings/angular bendings were weighted
by its B3LYP-D3/aug-cc-pVDZ populations for b) ΔE populations; c) ΔH populations and d) ΔG
populations. e) Theoretical spectrum using B3LYP-D3/aug-cc-pVDZ geometries and populations
obtained from the deconvolved experimental spectrum.
S42
CF3-C(O)-Gly-NHMe in Acetonitrile
a)
3480 3450 3420 3390 3360 3330 3300 3270 3240
0.00
0.02
0.04
0.06
0.08
0.10
0.12
Experimental Spectrum
Ab
sorb
an
ce
Wavenumber (cm-1)
b)
3480 3450 3420 3390 3360 3330 3300 3270 3240
0.00
0.02
0.04
0.06
0.08
0.10
0.12
2d
2b
P(2d) = 56.3%
Original SpectrumSum of deconvolved bandsDeconvolved 2bDeconvolved 2d
Ab
sorb
an
ce
Wavenumber (cm-1)
P(2b) = 43.7%
c)
3640 3620 3600 3580 3560 3540 3520 3500
0
100
200
300
400
500
600
Ep
isilo
n
Deconvolved 2bDeconvolved 2d
Wavenumber (cm-1)
P(2b) = 64.7%
P(2d) = 17.8%
d)
3640 3620 3600 3580 3560 3540 3520 3500
0
100
200
300
400
500
600
Ep
isilo
nDeconvolved 2bDeconvolved 2d
Wavenumber (cm-1)
P(2b) = 70.7%
P(2d) = 14.8%
e)
3640 3620 3600 3580 3560 3540 3520 3500
0
100
200
300
400
500
600
700
800
Ep
isilo
n
Wavenumber (cm-1)
Conformer 2bConformer 2d
P(2b) = 84.6%
P(2d) = 11.0%
f)
3640 3620 3600 3580 3560 3540 3520
0
100
200
300
400
Ep
isilo
n
Wavenumber (cm-1)
P(2b) = 43.7%
Conformer 2bConformer 2d
P(2d) = 56.3%
Figure S18: CF3-C(O)-Gly-NHMe N-H stretchings region (Amide A and B bands) in acetonitrile
of: a) IR experimental spectrum b) Deconvolved experimental Spectrum. Each conformer N-H
stretchings were weighted by its B3LYP-D3/aug-cc-pVDZ populations for c) ΔE populations; d)
ΔH populations and e) ΔG populations. f) Theoretical spectrum using B3LYP-D3/aug-cc-pVDZ
geometries and populations obtained from the deconvolved experimental spectrum..
S43
a)
1760 1740 1720 1700 1680 1660
0.0
0.1
0.2
0.3
0.4A
bso
rba
nce
Wavenumber (cm-1)
b)
1750 1700 1650 1600 1550
0
200
400
600
800
1000
1200
1400
1600
Conformer 2bConformer 2d
P(2b) = 64.7%
Ab
so
rba
nce
Wavenumber (cm-1)
P(2d) = 17.8%
c)
1750 1700 1650 1600 1550
0
200
400
600
800
1000
1200
1400
1600
Epis
ilon
Wavenumber (cm-1)
Conformer 2bConformer 2d
P(2b) = 70.7%
P(2d) = 14.8%
d)
1750 1700 1650 1600 1550
0
200
400
600
800
1000
1200
1400
1600
1800
2000
Ep
isilo
nConformer 2bConformer 2d
P(2b) = 84.6%
Wavenumber (cm-1)
P(2d) = 11.0%
e)
1750 1700 1650 1600 1550 1500
0
200
400
600
800
1000
1200
Ep
isilo
n
Conformer 2bConformer 2d
P(2b) = 43.7%
Wavenumber (cm-1)
P(2d) = 56.3%
Figure S19: CF3-C(O)-Gly-NHMe C=O stretchings region (~1700 cm-1; Amide I bands) and mix
of C(O)-N-H bond angle deformation/C-N bond stretching (~1550 cm-1; Amide II) in acetonitrile
of: a) IR experimental spectrum. Each conformer bond stretchings/angular bendings were
weighted by its B3LYP-D3/aug-cc-pVDZ populations for b) ΔE populations; c) ΔH populations
and d) ΔG populations. e) Theoretical spectrum using B3LYP-D3/aug-cc-pVDZ geometries and
populations obtained from the deconvolved experimental spectrum.
S44
Ac-Gly-N(Me)2 in CH2Cl2
a)
3500 3480 3460 3440 3420 3400 3380 3360 3340
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
Experimental Spectrum
Ab
so
rban
ce
Wavenumber (cm-1)
b)
3500 3480 3460 3440 3420 3400 3380 3360 3340
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
3d
3b
P(3d) = 6.6%
Experimental SpectrumSum of deconvolded bandsDeconvolved 3aDeconvolved 3d
P(3b) = 93.4%
Abso
rba
nce
Wavenumber (cm-1)
c)
3640 3620 3600 3580 3560 3540 3520 3500
0
100
200
300
400
500
600
Ep
isilo
n
Wavenumber (cm-1)
Conformer 3aConformer 3bConformer 3cConformer 3d
P(3a) = 93.9%
P(3b) = 4.3%
P(3c) = 1.2%P(3d) = 0.3%
d)
3640 3620 3600 3580 3560 3540 3520 3500
0
100
200
300
400
500
600E
pis
ilon
Wavenumber (cm-1)
Conformer 3aConformer 3bConformer 3cConformer 3d
P(3a) = 93.6%
P(3b) = 2.6%
P(3c) = 3.2%
P(3d) = 0.3%
e)
3640 3620 3600 3580 3560 3540 3520 3500
0
100
200
300
400
500
600
Ep
isilo
n
Wavenumber (cm-1)
Conformer 3aConformer 3bConformer 3cConformer 3d
P(3a) = 98.9%
P(3b) = 0.7%
P(3c) = 0.2%P(3d) = 0.1%
f)
3640 3620 3600 3580 3560 3540 3520 3500
0
100
200
300
400
500
Ep
isilo
n
Wavenumber (cm-1)
Conformer 3aConformer 3d
P(3a) = 93.4%
P(3d) = 6.6%
Figure S20: Ac-Gly-(NMe)2 N-H stretchings region (Amide A and B bands) in CH2Cl2 of: a) IR
experimental spectrum b) Deconvolved experimental Spectrum. Each conformer N-H stretchings
were weighted by its B3LYP-D3/aug-cc-pVDZ populations for c) ΔE populations; d) ΔH
populations and e) ΔG populations. f) Theoretical spectrum using B3LYP-D3/aug-cc-pVDZ
geometries and populations obtained from the deconvolved experimental spectrum
S45
a)
1720 1680 1640 1600 1560 1520 1480
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
Experimental Spectrum
Ab
sorb
an
ce
Wavenumber (cm-1)
b)
1700 1680 1660 1640 1620 1600 1580 1560 1540 1520
0
500
1000
1500
2000
2500
3000
3500
Conformer 3a
P(1a) = 93.9%
Ab
sorb
ance
Wavenumber (cm-1)
c)
1700 1680 1660 1640 1620 1600 1580 1560 1540 1520
0
500
1000
1500
2000
2500
3000
3500
Ep
isilo
n
Conformer 3a
P(3a) = 93.6%
Wavenumber (cm-1)
d)
1700 1680 1660 1640 1620 1600 1580 1560 1540 1520
0
500
1000
1500
2000
2500
3000
3500
Epis
ilon
Conformer 3a
P(3a) = 98.9%
Wavenumber (cm-1)
e)
1700 1680 1660 1640 1620 1600 1580 1560 1540 1520 1500
0
500
1000
1500
2000
2500
3000
Ep
isilo
n
Conformer 3aConformer 3d
P(3a) = 93.4%
Wavenumber (cm-1)
P(3d) = 6.6%
Figure S21: Ac-Gly-(NMe)2 C=O stretchings region (~1700 cm-1; Amide I bands) and mix of
C(O)-N-H bond angle deformation/C-N bond stretching (~1550 cm-1; Amide II) in CH2Cl2 of: a)
IR experimental spectrum. Each conformer bond stretchings/angular bendings were weighted by
its B3LYP-D3/aug-cc-pVDZ populations for b) ΔE populations; c) ΔH populations and d) ΔG
populations. e) Theoretical spectrum using B3LYP-D3/aug-cc-pVDZ geometries and populations
obtained from the deconvolved experimental spectrum.
S46
Ac-Gly-N(Me)2 in Acetonitrile
a)
3480 3460 3440 3420 3400 3380 3360 3340 3320 3300
0.00
0.01
0.02
0.03
0.04
0.05
0.06
Ab
sorb
an
ce
Wavenumber (cm-1)
b)
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Epis
ilon
Wavenumber (cm-1)
Conformer 3aConformer 3bConformer 3cConformer 3d
P(3a) = 90.6%
P(3b) = 5.1%
P(3d) = 0.9%P(3c) = 2.3%
c)
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isilo
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Wavenumber (cm-1)
Conformer 3aConformer 3bConformer 3cConformer 3d
P(3a) = 89.6%
P(3b) = 3.1%
P(3c) = 5.8%P(3d) = 0.6%
d)
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Ep
isilo
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Wavenumber (cm-1)
Conformer 3aConformer 3bConformer 3cConformer 3d
P(3a) = 98.5%
P(3b) = 0.8%
P(3c) = 0.3%P(3d) = 0.2%
Figure S22: Ac-Gly-(NMe)2 N-H stretchings region in acetonitrile of: a) IR experimental
spectrum b) ΔE populations; c) ΔH populations and d) ΔG populations.
S47
a)
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Wavenumber (cm-1)
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Wavenumber (cm-1)
Conformer 3aConformer 3bConformer 3cConformer 3d
P(3a) = 90.6%
P(3b) = 5.1%
P(3c) = 2.3%P(3d) = 0.9%
c)
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Wavenumber (cm-1)
Conformer 3aConformer 3bConformer 3cConformer 3d
P(3a) = 89.6%
P(3b) = 3.1%
P(3c) = 5.8%P(3d) = 0.6%
d)
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Wavenumber (cm-1)
Conformer 3aConformer 3bConformer 3cConformer 3d
P(3a) = 89.6%
P(3b) = 3.1%
P(3c) = 5.8%P(3d) = 0.6%
Figure S23: Ac-Gly-(NMe)2 C=O stretchings region (~1700 cm-1; Amide I bands) and mix of
C(O)-N-H bond angle deformation/C-N bond stretching (~1550 cm-1; Amide II) in acetonitrile of:
a) IR experimental spectrum. Each conformer bond stretchings/angular bendings were weighted
by its B3LYP-D3/aug-cc-pVDZ populations for b) ΔE populations; c) ΔH populations and d) ΔG
populations.