lower-rim calix[4]arene amide derivatives a comprehensive … · 2017-08-09 · a comprehensive...
TRANSCRIPT
A Comprehensive Study of Alkali Metal Cations Complexation by
Lower-Rim Calix[4]arene Amide Derivatives
ELECTRONIC SUPPLEMENTARY INFORMATION
Gordan Horvat,*a Leo Frkanec,b Nikola Cindroa and Vladislav Tomišić*a
a Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb,
Croatiab Laboratory for Supramolecular Chemistry, Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička cesta 54, 10000 Zagreb, Croatia
* Authors to whom correspondence should be addressed (E-mail: [email protected], [email protected])
1
Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.This journal is © the Owner Societies 2017
Table S1. Experimental 1H NMR chemical shifts of compound L1.
Solvent
CDCl3 CD3CN CD3OD
L1 protons
/ ppm
Ar-H 6.74, s, (8 H) 7.07, s, (8 H) 6.80, s (8, H)
OCH2 4.97, s, (8 H) 5.00, s, (8 H) 4.95, s, (8 H)
Calix-CHax5.19, d, 2J=12.9
Hz, (4 H)5.21, d, 2J=12.6
Hz, (4 H)4.92, d, 2J=12.7
Hz, (4 H)
Calix-CHeq 3.10–3.30a, d 3.16–3.30a, d 3.14, d, 2J=12.9 Hz, (4 H)
C(CH3)3 1.06, s, (36 H) 1.16, s, (36 H) 1.09, s, (36 H)
a the signals of these protons were overlapping with those bound to amide substituent alpha carbon atoms
2
Figure S1. a) 1H NMR and b) 13C NMR spectra of NaL2+ in deuterated chloroform at 25 oC.
3
a)
b)
Figure S2. Structures of a) L1 b) L1MeCN and c) L1MeOH adducts obtained by MD
simulations at 25 oC. Hydrogen atoms are omitted for clarity.
4
a) b)
c)
Figure S3. Structures of a) Z–L2 b) Z–L2MeCN and c) Z–L2MeOH adducts obtained by MD
simulations at 25 oC. Hydrogen atoms are omitted for clarity.
5
a) b)
c)
Figure S4. Structures of a) E–L2 b) E–L2MeCN and c) E–L2MeOH adducts obtained by MD
simulations at 25 oC. Hydrogen atoms are omitted for clarity.
6
a) b)
c)
Complexation of L1 in MeCN
0 20 40 60 80 100
50
52
54
56
58
60
62
a)
P /
W
t / min0.0 0.4 0.8 1.2 1.6 2.0
-0.4
-0.3
-0.2
-0.1
0.0
b)
(H
) / m
Jn(Rb+) / n(L1)
Figure S5. a) Microcalorimetric titration of L1 (c = 7.59 10–5 mol dm–3, V = 1.4182 cm3) with
RbNO3 (c = 8.19 10–4 mol dm3) in acetonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Rb+)/n(L1) ratio. ■ experimental; — calculated.
0 20 40 60 80 100 120 140 160 180 200 220
54
55
56
57
58
59
60
61
a)
P /
W
t / min0.0 0.4 0.8 1.2 1.6 2.0
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0.0
b)
(H
) / m
J
n(Na+) / n(KL1+)
Figure S6. a) Microcalorimetric titration of KL1+ (c = 3.24 10–4 mol dm–3, V = 1.4182 cm3)
with NaClO4 (c = 3.07 10–3 mol dm–3) in acetonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Na+)/n(KL1+) ratio. ■ experimental; — calculated.
7
20 40 60 80 100 120
45
50
55
60
a)
P /
W
t / min0.0 0.3 0.6 0.9 1.2 1.5 1.8 2.1 2.4
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0.0
b)
(H
) / m
J
n(Na+) / n(LiL1+)
Figure S7. a) Microcalorimetric titration of LiL1+ (c = 2.88 10–4 mol dm–3, V = 1.4182 cm3)
with NaClO4 (c = 3.19 10–3 mol dm–3) in acetonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Na+)/n(LiL1+) ratio. ■ experimental; — calculated.
250 260 270 280 290 3000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
a)A
/ nm0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
n(Li+) / n(L1)
b)A279nm
Figure S8. a) Spectrophotometric titration of L1 (c = 2.71 10–4 mol dm3, V0 = 2.0 cm3) with
LiClO4 (c = 1.00 10–3 mol dm3) in acetonitrile. l = 1 cm, t = 25.0 oC. Spectra are corrected for
dilution. b) Dependence of absorbance at 279 nm on n(Li+) / n(L1) ratio.
8
250 260 270 280 290 3000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
a)A
/ nm0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
n(Na+) / n(L1)
b)A279nm
Figure S9. a) Spectrophotometric titration of L1 (c = 2.71 10–4 mol dm3, V0 = 2.0 cm3) with
NaClO4 (c = 1.00 10–3 mol dm3) in acetonitrile. l = 1 cm, t = 25.0 oC. Spectra are corrected for
dilution. b) Dependence of absorbance at 279 nm on n(Na+) / n(L1) ratio.
250 260 270 280 290 3000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
a)A
/ nm0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
n(K+) / n(L1)
b)A279nm
Figure S10. a) Spectrophotometric titration of L1 (c = 2.71 10–4 mol dm3, V0 = 2.0 cm3) with
KClO4 (c = 1.00 10–3 mol dm–3) in acetonitrile. l = 1 cm, t = 25.0 oC. Spectra are corrected for
dilution. b) Dependence of absorbance at 279 nm on n(K+) / n(L1) ratio.
9
250 260 270 280 290 3000.0
0.2
0.4
0.6
0.8
1.0
a)A
/ nm0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
0.5
0.6
0.7
0.8
0.9
1.0
n(Rb+) / n(L1)
b)A279nm
Figure S11. a) Spectrophotometric titration of L1 (c = 1.96 10–4 mol dm–3, V0 = 2.0 cm3) with
RbNO3 (c = 8.54 10–4 mol dm–3) in acetonitrile. l = 1 cm, t = 25.0 oC. Spectra are corrected for
dilution. b) Dependence of absorbance at 279 nm on n(Rb+) / n(L1) ratio.
7.5 7.0 6.5 5.5 5.0 4.5 4.0
O
N
O
H
H
t-Bu
4
a
b
c
a
1.50
1.00
0.75
0.50
0.25
/ ppm
n(Li+) / n(L1)
0.00
b c
Figure S12. 1H NMR titration of L1 (c = 2.15 10–4 mol dm–3) with LiClO4 (c = 1.04 10–3 mol
dm–3) in CD3CN; t = 25 °C.
10
7.5 7.0 6.5 5.5 5.0 4.5 4.0
O
N
O
H
H
t-Bu
4
a
b
c
1.50
1.00
0.75
0.50
0.25
/ ppm
n(Na+) / n(L1)
0.00
b a c
Figure S13. 1H NMR titration of L1 (c = 2.15 10–4 mol dm–3) with NaClO4 (c = 1.08 10–3
mol dm–3) in CD3CN; t = 25 °C.
7.5 7.0 6.5 5.5 5.0 4.5 4.0
O
N
O
H
H
t-Bu
4
a
b
c
1.49
1.00
0.75
0.50
0.25
/ ppm
n(K+) / n(L1)
0.00
b a c
Figure S14. 1H NMR titration of L1 (c = 2.15 10–4 mol dm–3) with KClO4 (c = 0.97 10–3 mol
dm–3) in CD3CN; t = 25 °C.
11
7.5 7.0 6.5 5.5 5.0 4.5 4.0
O
N
O
H
H
t-Bu
4
a
b
c
1.46
0.97
0.73
0.49
0.24
/ ppm
n(Rb+) / n(L1)
0.00
b a c
Figure S15. 1H NMR titration of L1 (c = 2.15 10–4 mol dm–3) with RbNO3 (c = 2.85 10–3 mol
dm–3) in CD3CN; t = 25 °C.
Table S2. Energies of interactions of L1 with lithium, sodium and potassium cations and
acetonitrile, occurrence time ratio of different chemical species, and the number of carbonyl groups
which coordinate metal cation in the complexes obtained by MD simulations in acetonitrile at 25 oC;
dref = 7,85 Å.a
Li+ Na+ K+
LiL1+ LiL1MeCN+ NaL1+ NaL1MeCN+ KL1+ KL1MeCN+
E(M+–L) / kJ mol–1 –507 –516 –452 –454 –347 –348E(L–MeCN) / kJ mol–1 –549 –599 –543 –591 –546 –592E(L–MeCNincl) / kJ mol–1 – –50 – –50 – –50E(M+–MeCN) / kJ mol–1 –17 –15 –17 –12 –15 –10E(M+–MeCNincl) / kJ mol–1 – 9 – 8 – 7ttotal / ns 50 50 50t / ttotal 0.011 0.984 0.008 0.992 0.014 0.986N(coordination) 2.2 2.5 3.8 3.8 3.9 3.9N(MeCNincl) – 6 – 4 – 5
/ Åd 7.218.32
7.847.95
7.767.85
7.767.85
7.427.97
7.777.84
|d – dref| / Å0.530.71
0.230.25
0.210.21
0.200.22
0.390.54
0.200.21
σ(d) / Å 0.400.56
0.290.30
0.250.26
0.260.26
0.470.52
0.250.25
12
Figure S16. Structures of a) LiL1MeCN+, b) NaL1MeCN+ and c) KL1MeCN+ obtained by MD
simulations in acetonitrile at 25 oC. Hydrogen atoms are omitted for clarity.
13
b)a)
c)
Table S3. Energies of interactions of L1 with rubidium and caesium cations and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in acetonitrile at 25 oC;
dref = 7,85 Å.a
Rb+ Cs+
RbL1+ RbL1MeCN+ CsL1+ CsL1MeCN+
E(M+–L) / kJ mol–1 –309 –308 –253 –250E(L–MeCN) / kJ mol–1 –532 –594 –541 –595E(L–MeCNincl) / kJ mol–1
E(M+–MeCN) / kJ mol–1 –13 –9 –17 –26E(M+–MeCNincl) / kJ mol–1 – 7 – 6ttotal / ns 50 50t / ttotal 0.011 0.989 0.018 0.982N(coordination) 3.9 3.9 3.9 3.8N(MeCNincl) – 5 – 3
/ Åd 7.657.67
7.787.78
7.447.78
7.747.77
|d – dref| / Å0.430.44
0.210.21
0.500.62
0.220.23
σ(d) / Å 0.530.53
0.250.25
0.620.68
0.260.26
Figure S17. Structures of a) RbL1MeCN+ and b) CsL1MeCN+ obtained by MD simulations in
acetonitrile at 25 oC. Hydrogen atoms are omitted for clarity.
14
b)a)
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.60
5
10
15
20
25
30
35
Rela
tive
occu
panc
y / %
LiL1MeCN+
NaL1MeCN+
KL1MeCN+
RbL1MeCN+
CsL1MeCN+
d(OM+) / Ao
Figure S18. Distribution of metal cation-carbonyl oxygen bond length for M+–L1MeCN
complexes in acetonitrile obtained by MD simulations.
90 95 100 105 110 115 120 125 130 135 140 145 1500
5
10
15
20
25
Rela
tive
occu
panc
y / %
LiL1MeCN+
NaL1MeCN+
KL1MeCN+
RbL1MeCN+
CsL1MeCN+
(COM+) / o
Figure S19. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for M+–
L1MeCN complexes in acetonitrile obtained by MD simulations.
15
Complexation of L2 in MeCN
20 30 40 50 60 70 80 90 100
20
30
40
50
60
a)
P /
W
t / min0.3 0.6 0.9 1.2 1.5 1.8
-1.5
-1.2
-0.9
-0.6
-0.3
0.0
b)
(H
) / m
Jn(K+) / n(RbL2+)
Figure S20. a) Microcalorimetric titration of RbL2+ (c = 4.18 10–4 mol dm–3, V = 1.4182 cm3)
with KClO4 (c = 5.73 10–3 mol dm–3) in acetonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(K+)/n(RbL2+) ratio. ■ experimental; — calculated.
0 20 40 60 80 100 120 140
42
45
48
51
54
57
a)
P /
W
t / min0.0 0.4 0.8 1.2 1.6 2.0
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
b)
(H
) / m
J
n(Na+) / n(KL2+)
Figure S21. a) Microcalorimetric titration of KL2+ (c = 5.39 10–4 mol dm–3, V = 1.4182 cm3)
with NaClO4 (c = 5.92 10–3 mol dm–3) in acetonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Na+)/n(KL2+) ratio. ■ experimental; — calculated.
16
20 40 60 80 100 120
45
50
55
60
a)
P /
W
t / min0.0 0.3 0.6 0.9 1.2 1.5 1.8
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
b)
(H
) / m
J
n(Na+) / n(LiL2+)
Figure S22. a) Microcalorimetric titration of LiL2+ (c = 5.01 10–4 mol dm–3, V = 1.4182 cm3)
with NaClO4 (c = 5.62 10–3 mol dm–3) in acetonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Na+)/n(LiL2+) ratio. ■ experimental; — calculated.
Table S4. Enthalpies of complexation of L1 and L2 with lithium, sodium and potassium cations
in acetonitrile obtained by direct calorimetric titrations.
r
1
SEkJ mol
H
Li+ Na+ K+
L1 –55.5 0.8 –70.1 0.7 –55.4 0.7
L2 –44.4 0.3 –66.8 0.4 –49.6 0.2
17
250 260 270 280 290 3000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
a)A
/ nm0.0 0.3 0.6 0.9 1.2 1.5 1.8
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
n(Li+) / n(L2)
b)A279nm
Figure S23. a) Spectrophotometric titration of L2 (c = 3.13 10–4 mol dm–3, V0 = 2.0 cm3) with
LiClO4 (c = 1.50 10–3 mol dm–3) in acetonitrile. l = 1 cm, t = 25.0 oC. Spectra are corrected for
dilution. b) Dependence of absorbance at 279 nm on n(Li+) / n(L2) ratio.
250 260 270 280 290 3000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
a)A
/ nm0.0 0.3 0.6 0.9 1.2 1.5 1.8
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
n(Na+) / n(L2)
b)A279nm
Figure S24. a) Spectrophotometric titration of L2 (c = 3.13 10–4 mol dm–3, V0 = 2.0 cm3) with
NaClO4 (c = 1.50 10–3 mol dm–3) in acetonitrile. l = 1 cm, t = 25.0 oC. Spectra are corrected for
dilution. b) Dependence of absorbance at 279 nm on n(Na+) / n(L2) ratio.
18
250 260 270 280 290 3000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
a)A
/ nm0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
n(K+) / n(L2)
b)A279nm
Figure S25. a) Spectrophotometric titration of L2 (c = 3.13 10–4 mol dm–3, V0 = 2.0 cm3) with
KClO4 (c = 1.50 10–3 mol dm–3) in acetonitrile. l = 1 cm, t = 25.0 oC. Spectra are corrected for
dilution. b) Dependence of absorbance at 279 nm on n(K+) / n(L2) ratio.
260 270 280 290 3000.00
0.03
0.06
0.09
0.12
0.15
0.18
0.21a)A
/ nm0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
0.12
0.14
0.16
0.18
0.20
n(Rb+) / n(L2)
b)A279nm
Figure S26. a) Spectrophotometric titration of L2 (c = 1.52 10–5 mol dm–3, V0 = 27 cm3) with
RbNO3 (c = 6.97 10–4 mol dm–3) in acetonitrile. l = 10 cm, t = 25.0 oC. Spectra are corrected for
dilution. b) Dependence of absorbance at 279 nm on n(Rb+) / n(L2) ratio. ■ experimental;
― calculated.
19
7.5 7.0 1.5 1.0 0.5
O
N
O
H
H
t-Bu
4
a
b1.61
0.54
/ ppm
n(Li+) / n(L2)
0.00b
a
Figure S27. 1H NMR titration of L2 (c = 5.80 10–4 mol dm–3) with LiClO4
(c = 0.0124 mol dm–3) in CD3CN; t = 25 °C.
7.5 7.0 1.5 1.0 0.5
O
N
O
H
H
t-Bu
4
a
b1.58
0.53
/ ppm
n(Na+) / n(L2)
0.00b
a
Figure S28. 1H NMR titration of L2 (c = 5.80 10–4 mol dm–3) with NaClO4
(c = 9.15 10–3 mol dm–3) in CD3CN; t = 25 °C.
20
7.5 7.0 1.5 1.0 0.5
O
N
O
H
H
t-Bu
4
a
b1.64
0.55
/ ppm
n(K+) / n(L2)
0.00b
a
Figure S29. 1H NMR titration of L2 (c = 5.80 10–4 mol dm–3) with KClO4
(c = 0.0161 mol dm–3) in CD3CN; t = 25 °C.
7.5 7.0 1.5 1.0 0.5
O
N
O
H
H
t-Bu
4
a
b3.50
0.54
/ ppm
n(Rb+) / n(L2)
0.00b
a
Figure S30. 1H NMR titration of L2 (c = 4.72 10–4 mol dm–3) with RbNO3
(c = 9.49 10–4 mol dm–3) in CD3CN; t = 25 °C.
21
Table S5. Energies of interactions of Z–L2 with lithium, sodium and potassium cations and
acetonitrile, occurrence time ratio of different chemical species, and the number of carbonyl groups
which coordinate metal cation in the complexes obtained by MD simulations in acetonitrile at 25 oC;
dref = 7,85 Å.a
Li+ Na+ K+
LiZ–L2+ LiZ–L2MeCN+ NaZ–L2+ NaZ–L2MeCN+ KZ–L2+ KZ–L2MeCN+
E(M+–L) / kJ mol–1 –506 –511 –442 –445 –341 –341E(L–MeCN) / kJ mol–1 –467 –520 –463 –515 –461 –517E(L–MeCNincl) / kJ mol–1 – –52 – –51 – –50E(M+–MeCN) / kJ mol–1 –26 –20 –21 –16 –18 –13E(M+–MeCNincl) / kJ mol–1 – 9 – 8 – 8ttotal / ns 50 50 50t / ttotal 0.009 0.991 0.016 0.984 0.018 0.982N(coordination) 2.3 2.6 3.8 3.9 3.91 3.94N(MeCNincl) – 3 – 3 – 3
/ Åd 7.637.84
7.827.95
7.627.88
7.827.87
7.647.77
7.807.81
|d – dref| / Å0.630.68
0.240.25
0.350.42
0.210.21
0.410.44
0.200.20
σ(d) / Å 0.750.76
0.290.30
0.440.50
0.260.26
0.530.53
0.250.25
Table S6. Energies of interactions of Z–L2 with rubidium and caesium cations and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in acetonitrile at 25 oC;
dref = 7,85 Å.a
Rb+ Cs+
RbZ–L2+ RbZ–L2MeCN+ CsZ–L2+ CsZ–L2MeCN+
E(M+–L) / kJ mol–1 –306 –304 –250 –252E(L–MeCN) / kJ mol–1 –478 –524 –493 –539E(L–MeCNincl) / kJ mol–1 – –50 – –51E(M+–MeCN) / kJ mol–1 –14 –12 –29 –26E(M+–MeCNincl) / kJ mol–1 – 7 – 6ttotal / ns 50 50t / ttotal 0.012 0.988 0.085 0.915N(coordination) 3.95 3.94 3.77 3.84N(MeCNincl) – 4 – 4
/ Åd 7.627.72
7.787.78
7.497.74
7.747.75
|d – dref| / Å0.420.46
0.210.21
0.540.62
0.220.22
σ(d) / Å 0.520.54
0.250.25
0.680.71
0.250.25
22
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.60
5
10
15
20
25
30
35
Rela
tive
occu
panc
y / %
d(OM+) / A
LiZL2MeCN+
NaZL2MeCN+
KZL2MeCN+
RbZL2MeCN+
CsZL2MeCN+
o
Figure S31. Distribution of metal cation-carbonyl oxygen bond length for M+–Z–L2MeCN
complexes in acetonitrile obtained by MD simulations.
90 95 100 105 110 115 120 125 130 135 140 145 1500
5
10
15
20
25
30
Rela
tive
occu
panc
y / %
LiZL2MeCN+
NaZL2MeCN+
KZL2MeCN+
RbZL2MeCN+
CsZL2MeCN+
(COM+) / o
Figure S32. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for
M+–Z–L2MeCN complexes in acetonitrile obtained by MD simulations.
23
Table S7. Energies of interactions of E–L2 with lithium, sodium and potassium cations and
acetonitrile, occurrence time ratio of different chemical species, and the number of carbonyl groups
which coordinate metal cation in the complexes obtained by MD simulations in acetonitrile at 25 oC;
dref = 7,85 Å.a
Li+ Na+ K+
LiE–L2+ LiE–L2MeCN+ NaE–L2+ NaE–L2MeCN+ KE–L2+ KE–L2MeCN+
E(M+–L) / kJ mol–1 –489 –497 –b –445 – –344E(L–MeCN) / kJ mol–1 –494 –545 – –558 – –549E(L–MeCNincl) / kJ mol–1 – –51 – –51 – –51E(M+–MeCN) / kJ mol–1 –23 –17 – –7 – –7E(M+–MeCNincl) / kJ mol–1 – 9 – 8 – 8ttotal / ns 50 50 50t / ttotal 0.007 0.993 0 1 0.001 0.999N(coordination) 2.10 2.28 – 3.83 – 3.93N(MeCNincl) – 4 – 1 – 2
/ Åd 7.028.48
7.837.94 – 7.84
7.847.707.78
7.807.80
|d – dref| / Å0.630.84
0.250.26 – 0.21
0.210.260.26
0.200.20
σ(d) / Å 0.330.50
0.310.31 – 0.26
0.260.300.31
0.250.25
Table S8. Energies of interactions of E–L2 with rubidium and caesium cations and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in acetonitrile at 25 oC;
dref = 7,85 Å.a
Rb+ Cs+
RbE–L2+ RbE–L2MeCN+ CsE–L2+ CsE–L2MeCN+
E(M+–L) / kJ mol–1 –308 –303 –248 –242E(L–MeCN) / kJ mol–1 –507 –547 –476 –529E(L–MeCNincl) / kJ mol–1 – –49 – –50E(M+–MeCN) / kJ mol–1 –11 –13 –35 –39E(M+–MeCNincl) / kJ mol–1 – 7 – 5ttotal / ns 50 50t / ttotal 0.024 0.976 0.035 0.965N(coordination) 3.91 3.93 3.86 3.82N(MeCNincl) – 3 – 1
/ Åd 7.657.69
7.787.78
7.108.07
7.757.76
|d – dref| / Å0.480.49
0.210.21
0.550.87
0.220.22
σ(d) / Å 0.590.59
0.250.25
0.630.71
0.260.26
24
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.60
5
10
15
20
25
30
35
Rela
tive
occu
panc
y / %
d(OM+) / A
LiEL2MeCN+
NaEL2MeCN+
KEL2MeCN+
RbEL2MeCN+
CsEL2MeCN+
o
Figure S33. Distribution of metal cation-carbonyl oxygen bond length for M+–E–L2MeCN
complexes in acetonitrile obtained by MD simulations.
90 95 100 105 110 115 120 125 130 135 140 145 1500
5
10
15
20
25
30
Rela
tive
occu
panc
y / %
LiEL2MeCN+
NaEL2MeCN+
KEL2MeCN+
RbEL2MeCN+
CsEL2MeCN+
(COM+) / o
Figure S34. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for
M+–E–L2MeCN complexes in acetonitrile obtained by MD simulations.
25
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
-3
-2
-1
0
1
2
E
-Z(R
elat
ive o
ccup
ancy
) / %
d(OM+) / A
LiL2MeCN+
NaL2MeCN+
KL2MeCN+
RbL2MeCN+
CsL2MeCN+
o
Figure S35. Difference in the distribution of metal cation-carbonyl oxygen bond length between
E–L2 and L2–Z alkali-metal cation complexes in acetonitrile obtained by MD simulations.
90 95 100 105 110 115 120 125 130 135 140 145 150-6
-5
-4
-3
-2
-1
0
1
2
3
4
5
E-Z(R
elat
ive o
ccup
ancy
) / %
LiL2MeCN+
NaL2MeCN+
KL2MeCN+
RbL2MeCN+
CsL2MeCN+
(COM+) / o
Figure S36. Difference in the distribution of metal cation-carbonyl oxygen-carbonyl carbon
angle between E–L2 and L2–Z alkali-metal cation complexes in acetonitrile obtained by MD
simulations.
26
L1 in PhCN
10 20 30 40 50 60 70 80 90 100
50
51
52
53
54
55
56
57
58
a)
P /
W
t / min1 2 3 4 5
-0.5
-0.4
-0.3
-0.2
-0.1
0.0
b)
(H
) / m
Jn(Cs+) / n(L1)
Figure S37. a) Microcalorimetric titration of L1 (c = 2.35 10–4 mol dm–3, V = 1.4182 cm3) with
CsBPh4 (c = 5.14 10–3 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Cs+) / n(L1) ratio. ■ experimental; — calculated.
0 10 20 30 40 50 60 70 80 90 10015
20
25
30
35
40
45
50
55
a)
P /
W
t / min0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00
-1.4
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
b)
(H
) / m
J
n(Rb+) / n(L1)
Figure S38. a) Microcalorimetric titration of L1 (c = 4.00 10–4 mol dm–3, V = 1.4182 cm3) with
RbBPh4 (c = 3.74 10–3 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Rb+) / n(L1) ratio. ■ experimental; — calculated.
27
10 20 30 40 50 60 70
20
25
30
35
40
45
50
a)
P /
W
t / min0.25 0.50 0.75 1.00 1.25 1.50 1.75
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
b)
(H
) / m
J
n(Na+) / n(KL1+)
Figure S39. a) Microcalorimetric titration of KL1+ (c = 4.50 10–4 mol dm–3, V = 1.4182 cm3)
with NaClO4 (c = 3.33 10–3 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Na+) / n(KL1+) ratio. ■ experimental; — calculated.
10 20 30 40 50 60 70 80 9005
1015202530354045505560
a)P /
W
t / min0 5 10 15 20 25 30 35 40 45
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
b)
(H
) / m
J
n(Na+) / n(LiL1+)
Figure S40. a) Microcalorimetric titration of LiL1+ (c = 4.02 10–4 mol dm–3, V = 1.4182 cm3)
with NaBPh4 (c = 7.81 10–2 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Na+) / n(LiL1+) ratio. ■ experimental; — calculated.
28
10 20 30 40 50 60 70 80 90 100 110
25
30
35
40
a)
P /
W
t / min0 100 200 300 400 500 600
-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
b)
(H
) / m
J
n(MeCN) / n(LiL1+)
Figure S41. a) Microcalorimetric titration of LiL1+ (c = 2.90 10–4 mol dm–3, V = 1.4182 cm3)
with MeCN (c = 1.00 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive enthalpy
change on n(MeCN) / n(LiL1+) ratio. ■ experimental; ― calculated.
20 40 60 80 100 120 140 160-15
-10
-5
0
5
10
15
20
25
30
35
a)
P /
W
t / min0 10 20 30 40 50 60 70 80
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
b)
(H
) / m
J
n(MeCN) / n(KL1+)
Figure S42. a) Microcalorimetric titration of KL1+ (c = 2.90 10–4 mol dm–3, V = 1.4182 cm3)
with MeCN (c = 0.100 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive enthalpy
change on n(MeCN) / n(KL1+) ratio. ■ experimental; ― calculated.
29
0 10 20 30 40 50 60 70 80 90 10042
44
46
48
50
52
54
56
58
a)
P /
W
t / min20 40 60 80 100 120
-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
b)
(H
) / m
J
n(MeCN) / n(RbL1+)
Figure S43. a) Microcalorimetric titration of RbL1+ (c = 1.74 10–4 mol dm–3, V = 1.4182 cm3)
with MeCN (c = 0.100 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive enthalpy
change on n(MeCN) / n(RL1+) ratio. ■ experimental; ― calculated.
Table S9. Energies of interactions of L1 with lithium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC; dref =
7,85 Å.a
LiL1+ LiL1PhCN'+ LiL1PhCN+ LiL1MeCN+
E(M+–L) / kJ mol–1 –513 –500 –516 –515E(L–PhCN) / kJ mol–1 –793 –819 –832 –804E(L–MeCNincl) / kJ mol–1 – – – –51E(M+–PhCN) / kJ mol–1 –14 –39 –11 –17E(M+–MeCNincl) / kJ mol–1 – – – 9ttotal / ns 50 25t / ttotal 0.705 0.075 0.220 1N(coordination) 2.29 1.90 2.32 2.47N(PhCNincl) – 7 26 –
/ Åd 7.418.00
8.038.16
7.948.24
7.758.02
|d – dref| / Å0.730.84
0.400.52
0.240.26
0.310.37
σ(d) / Å 0.840.89
0.330.34
0.470.48
0.280.28
30
Figure S44. Structures of a) LiL1PhCN'+ and b) LiL1PhCN+ obtained by MD simulations in
benzonitrile at 25 oC. Hydrogen atoms are omitted for clarity.
1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.5 2.60
5
10
15
20
25
30
Rela
tive
occu
panc
y / %
d(OM+) / A
LiL1+
LiL1PhCN'+
LiL1PhCN+
LiL1MeCN+
o
Figure S45. Distribution of metal cation-carbonyl oxygen bond length for Li+–L1 complexes in
benzonitrile obtained by MD simulations.
31
b)a)
95 100 105 110 115 120 125 130 135 140 145 150 1550
5
10
15
20
25 LiL1+
LiL1PhCN'+
LiL1PhCN+
LiL1MeCN+
Rela
tive
occu
panc
y / %
(COM+) / o
Figure S46. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for Li+–L1
complexes in benzonitrile obtained by MD simulations.
Table S10. Energies of interactions of L1 with sodium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC;
dref = 7,85 Å.a
NaL1+ NaL1PhCN'+ NaL1PhCN+ NaL1MeCN+
E(M+–L) / kJ mol–1 –447 –433 –453 –449E(L–PhCN) / kJ mol–1 –809 –839 –863 –813E(L–MeCNincl) / kJ mol–1 – – – –51E(M+–PhCN) / kJ mol–1 –14 –28 –11 –16E(M+–MeCNincl) / kJ mol–1 – – – 8ttotal / ns 50 50t / ttotal 0.949 0.006 0.045 1N(coordination) 3.43 2.06 3.76 3.81N(PhCNincl) – 2 32 –
/ Åd 7.657.84
7.978.01
7.908.00
7.847.84
|d – dref| / Å0.400.45
0.260.30
0.330.36
0.210.22
σ(d) / Å 0.550.52
0.300.32
0.420.42
0.270.27
32
Figure S47. Structures of a) NaL1PhCN'+ and b) NaL1PhCN+ obtained by MD simulations in
benzonitrile at 25 oC. Hydrogen atoms are omitted for clarity.
2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.00
5
10
15
20
Rela
tive
occu
panc
y / %
d(OM+) / A
NaL1+
NaL1PhCN'+
NaL1PhCN+
NaL1MeCN+
o
Figure S48. Distribution of metal cation-carbonyl oxygen bond length for Na+–L1 complexes in
benzonitrile obtained by MD simulations.
33
a) b)
90 95 100 105 110 115 120 125 130 135 140 1450
5
10
15
20
25
Rela
tive
occu
panc
y / %
NaL1+
NaL1PhCN'+
NaL1PhCN+
NaL1MeCN+
(COM+) / o
Figure S49. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for Na+–L1
complexes in benzonitrile obtained by MD simulations.
Table S11. Energies of interactions of L1 with potassium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC;
dref = 7,85 Å.a
KL1+ KL1PhCN'+ KL1PhCN+ KL1MeCN+
E(M+–L) / kJ mol–1 –349 –351 –349 –350E(L–PhCN) / kJ mol–1 –797 –833 –850 –795E(L–MeCNincl) / kJ mol–1 – – – –46E(M+–PhCN) / kJ mol–1 –11 –29 –11 7E(M+–MeCNincl) / kJ mol–1 – – – –13ttotal / ns 50 50t / ttotal 0.985 0.003 0.012 1N(coordination) 3.89 3.92 3.95 3.91N(PhCNincl) – 3 11 –
/ Åd 7.797.56
8.007.92
8.097.95
7.777.80
|d – dref| / Å0.430.50
0.260.21
0.370.34
0.240.23
σ(d) / Å 0.540.57
0.290.26
0.390.40
0.300.29
34
Figure S50. Structures of a) KL1PhCN'+ and b) KL1PhCN+ obtained by MD simulations in
benzonitrile at 25 oC. Hydrogen atoms are omitted for clarity.
2.4 2.5 2.6 2.7 2.8 2.9 3.0 3.10
5
10
15
20
25
Rela
tive
occu
panc
y / %
d(OM+) / A
KL1+
KL1PhCN'+
KL1PhCN+
KL1MeCN+
o
Figure S51. Distribution of metal cation-carbonyl oxygen bond length for K+–L1 complexes in
benzonitrile obtained by MD simulations.
35
a) b)
90 95 100 105 110 115 120 125 130 1350
5
10
15
20
25
Rela
tive
occu
panc
y / %
KL1+
KL1PhCN'+
KL1PhCN+
KL1MeCN+
(COM+) / o
Figure S52. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for K+–L1
complexes in benzonitrile obtained by MD simulations.
Table S12. Energies of interactions of L1 with rubidium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC;
dref = 7,85 Å.a
RbL1+ RbL1PhCN'+ RbL1PhCN+ RbL1MeCN+
E(M+–L) / kJ mol–1 –308 –295 –304 –309E(L–PhCN) / kJ mol–1 –789 –808 –843 –792E(L–MeCNincl) / kJ mol–1 – – – –50E(M+–PhCN) / kJ mol–1 –8 –13 –5 –14E(M+–MeCNincl) / kJ mol–1 – – – 7ttotal / ns 50 2.6t / ttotal 0.988 0.008 0.004 1N(coordination) 3.90 3.78 3.90 3.91N(PhCNincl) – 3 2 1
/ Åd 7.577.73
8.117.84
7.928.04
7.727.82
|d – dref| / Å0.520.47
0.300.23
0.360.37
0.230.21
σ(d) / Å 0.600.58
0.260.28
0.420.40
0.250.26
36
Figure S53. Structures of a) RbL1PhCN'+ and b) RbL1PhCN+ obtained by MD simulations in
benzonitrile at 25 oC. Hydrogen atoms are omitted for clarity.
2.5 2.6 2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.40
5
10
15
20
25
Rela
tive
occu
panc
y / %
d(OM+) / A
RbL1+
RbL1PhCN'+
RbL1PhCN+
RbL1MeCN+
o
Figure S54. Distribution of metal cation-carbonyl oxygen bond length for Rb+–L1 complexes in
benzonitrile obtained by MD simulations.
37
a) b)
90 95 100 105 110 115 120 125 130 1350
5
10
15
20
25
Rela
tive
occu
panc
y / %
RbL1+
RbL1PhCN'+
RbL1PhCN+
RbL1MeCN+
(COM+) / o
Figure S55. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for Rb+–L1
complexes in benzonitrile obtained by MD simulations.
38
L2 in PhCN
10 20 30 40 50 60 70 80 90 10054
55
56
57
58 a)
P /
W
t / min0.4 0.8 1.2 1.6 2.0
-0.20
-0.15
-0.10
-0.05
b)
(H
) / m
Jn(Cs+) / n(L2)
Figure S56. a) Microcalorimetric titration of L2 (c = 4.81 10–4 mol dm–3, V = 1.4182 cm3) with
CsBPh4 (c = 4.94 10–3 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Cs+) / n(L2) ratio. ■ experimental; — calculated.
10 20 30 40 50 60 70 80 90
25
30
35
40
45
50
55
a)
P /
W
t / min0.0 0.5 1.0 1.5 2.0
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
b)
(H
) / m
J
n(Rb+) / n(L2)
Figure S57. a) Microcalorimetric titration of L2 (c = 3.28 10–4 mol dm–3, V = 1.4182 cm3) with
RbBPh4 (c = 3.44 10–3 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Rb+) / n(L2) ratio. ■ experimental; — calculated.
39
20 30 40 50 60 70 80 90 100 11052.5
53.0
53.5
54.0
54.5
55.0
55.5
a)
P /
W
t / min0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
-0.10
-0.08
-0.06
-0.04
-0.02
0.00
b)
(H
) / m
J
n(K+) / n(L2)
Figure S58. a) Microcalorimetric titration of L2 (c = 2.13 10–5 mol dm–3, V = 1.4182 cm3) with
KSCN (c = 1.93 10–4 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(K+) / n(L2) ratio. ■ experimental; — calculated.
20 40 60 80 100 120 140 16040
42
44
46
48
50
52
54
56
a)
P /
W
t / min0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0.0
b)
(H
) / m
J
n(Na+) / n(KL2+)
Figure S59. a) Microcalorimetric titration of KL2+ (c = 3.44 10–4 mol dm–3, V = 1.4182 cm3)
with NaClO4 (c = 2.94 10–3 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Na+) / n(KL2+) ratio. ■ experimental; — calculated.
40
20 40 60 80 100 120 140 160-15
-10
-5
0
5
10
15
20
25
30
35
a)
P /
W
t / min0 10 20 30 40 50 60 70 80
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
b)
(H
) / m
J
n(Na+) / n(LiL2+)
Figure S60. a) Microcalorimetric titration of LiL2+ (c = 5.45 10–4 mol dm–3, V = 1.4182 cm3)
with NaBPh4 (c = 2.57 10–2 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(Na+) / n(LiL2+) ratio. ■ experimental; — calculated.
Table S13. Enthalpies of complexation of L1 and L2 with lithium, sodium and potassium cations
in benzonitrile obtained by direct calorimetric titrations.
r
1
SEkJ mol
H
Li+ Na+ K+
L1 –44.8 0.5 –55.3 0.5 –41.0 0.2
L2 –47.1 0.9 –60.8 0.5 –36.7 0.5
41
10 20 30 40 50 60 70 80 90 100
42
44
46
48
50
52
54
56
a)
P /
W
t / min0 100 200 300 400 500
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
b)
(H
) / m
J
n(MeCN) / n(LiL2+)
Figure S61. a) Microcalorimetric titration of LiL2+ (c = 3.14 10–4 mol dm–3, V = 1.4182 cm3)
with MeCN (c = 1.00 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive enthalpy
change on n(MeCN) / n(LiL2+) ratio. ■ experimental; ― calculated.
20 40 60 80 100 120 140 160-15
-10
-5
0
5
10
15
20
25
30
35
a)
P /
W
t / min0 10 20 30 40 50 60 70
-2.1
-1.8
-1.5
-1.2
-0.9
-0.6
-0.3
0.0
b)
(H
) / m
J
n(MeCN) / n(NaL2+)
Figure S62. a) Microcalorimetric titration of NaL2+ (c = 3.14 10–4 mol dm–3, V = 1.4182 cm3)
with MeCN (c = 0.100 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive
enthalpy change on n(MeCN) / n(NaL2+) ratio. ■ experimental; ― calculated.
42
20 40 60 80 100 120 140 160
30
35
40
45
50
55
a)
P /
W
t / min0 10 20 30 40 50 60 70
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
b)
(H
) / m
J
n(MeCN) / n(KL2+)
Figure S63. a) Microcalorimetric titration of KL2+ (c = 3.14 10–4 mol dm–3, V = 1.4182 cm3) with
MeCN (c = 0.100 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive enthalpy
change on n(MeCN) / n(KL2+) ratio. ■ experimental; ― calculated.
10 20 30 40 50 60 70 80 90 100
35
40
45
50
55
60
a)
P /
W
t / min0 10 20 30 40 50 60
-1.4
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
b)
(H
) / m
J
n(MeCN) / n(RbL2+)
Figure S64. a) Microcalorimetric titration of RbL2+ (c = 3.62 10–4 mol dm–3, V = 1.4182 cm3)
with MeCN (c = 0.100 mol dm–3) in benzonitrile; t = 25 °C; b) Dependence of successive enthalpy
change on n(MeCN) / n(RbL2+) ratio. ■ experimental; ― calculated.
43
Table S14. Energies of interactions of Z–L2 with lithium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC;
dref = 7,85 Å.a
LiZ–L2+ LiZ–L2PhCN'+ LiZ–L2PhCN+ LiZ–L2MeCN+
E(M+–L) / kJ mol–1 –501 –482 –506 –511E(L–PhCN) / kJ mol–1 –674 –681 –718 –662E(L–MeCNincl) / kJ mol–1 – – – –52E(M+–PhCN) / kJ mol–1 –18 –44 –16 –21E(M+–MeCNincl) / kJ mol–1 – – – 9ttotal / ns 43.5 17.5t / ttotal 0.848 0.006 0.146 1N(coordination) 2.22 1.66 2.40 2.58N(PhCNincl) – 3 27 –
/ Åd 7.457.95
8.088.12
8.068.13
7.748.00
|d – dref| / Å0.760.85
0.330.35
0.440.51
0.300.31
σ(d) / Å 0.870.89
0.330.35
0.500.53
0.250.27
Figure S65. Structures of a) LiZ–L2PhCN'+ and b) LiZ–L2PhCN+ obtained by MD simulations
in benzonitrile at 25 oC. Hydrogen atoms are omitted for clarity.
44
a) b)
1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.5 2.60
5
10
15
20
25
30
Rela
tive
occu
panc
y / %
d(OM+) / A
LiZL2+
LiZL2PhCN'+
LiZL2PhCN+
LiZL2MeCN+
o
Figure S66. Distribution of metal cation-carbonyl oxygen bond length for Li+–Z–L2 complexes
in benzonitrile obtained by MD simulations.
95 100 105 110 115 120 125 130 135 140 145 150 1550
5
10
15
20
25 LiZL2+
LiZL2PhCN'+
LiZL2PhCN+
LiZL2MeCN+
Rela
tive
occu
panc
y / %
(COM+) / o
Figure S67. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for Li+–Z–L2
complexes in benzonitrile obtained by MD simulations.
45
Table S15. Energies of interactions of Z–L2 with sodium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC; dref
= 7,85 Å.a
NaZ–L2+ NaZ– L2PhCN'+ NaZ– L2PhCN+ NaZ– L2MeCN+
E(M+–L) / kJ mol–1 –430 –441 –422 –444E(L–PhCN) / kJ mol–1 –650 –659 –695 –659E(L–MeCNincl) / kJ mol–1 – – – –52E(M+–PhCN) / kJ mol–1 –12 –25 –6 –18E(M+–MeCNincl) / kJ mol–1 – – – 8ttotal / ns 53 16.9t / ttotal 0.892 0.013 0.095 0.851N(coordination) 3.51 3.78 3.37 3.91N(PhCNincl) – 2 32 –
/ Åd 7.707.76
7.887.91
8.068.07
7.837.84
|d – dref| / Å0.430.44
0.390.39
0.380.39
0.210.21
σ(d) / Å 0.540.54
0.300.31
0.410.41
0.260.26
Figure S68. Structures of a) NaZ–L2PhCN'+ and b) NaZ–L2PhCN+ obtained by MD simulations
in benzonitrile at 25 oC. Hydrogen atoms are omitted for clarity.
46
a) b)
2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.0 3.10
5
10
15
20
25
Rela
tive
occu
panc
y / %
d(OM+) / A
NaZ3+
NaZ3PhCN'+
NaZ3PhCN+
NaZ3MeCN+
o
Figure S69. Distribution of metal cation-carbonyl oxygen bond length for Na+–Z–L2 complexes
in benzonitrile obtained by MD simulations.
90 95 100 105 110 115 120 125 130 1350
5
10
15
20
25
30
Rela
tive
occu
panc
y / %
NaZ3+
NaZ3PhCN'+
NaZ3PhCN+
NaZ3MeCN+
(COM+) / o
Figure S70. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for Na+–Z–L2
complexes in benzonitrile obtained by MD simulations.
47
Table S16. Energies of interactions of Z–L2 with potassium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC;
dref = 7,85 Å.a
KZ–L2+ KZ–L2PhCN'+ KZ–L2PhCN+ KZ–L2MeCN+
E(M+–L) / kJ mol–1 –342 – –344 –340E(L–PhCN) / kJ mol–1 –665 – –706 –670E(L–MeCNincl) / kJ mol–1 – – – –51.5E(M+–PhCN) / kJ mol–1 –13 – –13 –15E(M+–MeCNincl) / kJ mol–1 – – – 8ttotal / ns 44.5 25t / ttotal 0.988 0 0.002 –N(coordination) 3.95 – 3.93 3.96N(PhCNincl) – – 2 –
/ Åd 7.587.77
– 7.868.06
7.787.81
|d – dref| / Å0.450.50
– 0.290.36
0.210.21
σ(d) / Å 0.560.58
– 0.340.37
0.250.25
Figure S71. Structure KZ–L2PhCN+ obtained by MD simulations in benzonitrile at 25 oC.
Hydrogen atoms are omitted for clarity.
48
2.4 2.5 2.6 2.7 2.8 2.9 3.0 3.1 3.20
5
10
15
20
25
Rela
tive
occu
panc
y / %
d(OM+) / A
KZ3+
KZ3PhCN+
KZ3MeCN+
o
Figure S72. Distribution of metal cation-carbonyl oxygen bond length for K+–Z–L2 complexes
in benzonitrile obtained by MD simulations.
90 95 100 105 110 115 120 125 130 1350
5
10
15
20
25
Rela
tive
occu
panc
y / %
KZ3+
KZ3PhCN+
KZ3MeCN+
(COM+) / o
Figure S73. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for K+–Z–L2
complexes in benzonitrile obtained by MD simulations.
49
Table S17. Energies of interactions of Z–L2 with rubidium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC;
dref = 7,85 Å.a
RbZ–L2+ RbZ– L2PhCN'+ RbZ– L2PhCN+ RbZ– L2MeCN+
E(M+–L) / kJ mol–1 –304 –306 – –309E(L–PhCN) / kJ mol–1 –646 –701 – –664E(L–MeCNincl) / kJ mol–1 – – – –51E(M+–PhCN) / kJ mol–1 –9 –26 – –10E(M+–MeCNincl) / kJ mol–1 – – – 7ttotal / ns 10 7.3t / ttotal 0.953 0.047 0 1N(coordination) 3.97 3.99 – 3.99N(PhCNincl) – 1 – –
/ Åd 7.687.62
7.947.96
– 7.777.76
|d – dref| / Å0.510.53
0.250.25
– 0.210.22
σ(d) / Å 0.620.63
0.290.29
– 0.250.25
Figure S74. Structure RbZ–L2PhCN+ obtained by MD simulations in benzonitrile at 25 oC.
Hydrogen atoms are omitted for clarity.
50
2.5 2.6 2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.40
5
10
15
20
25
30
RbZL2+
RbZL2PhCN'+
RbZL2MeCN+
Rela
tive
occu
panc
y / %
d(OM+) / Ao
Figure S75. Distribution of metal cation-carbonyl oxygen bond length for Rb+–Z–L2 complexes
in benzonitrile obtained by MD simulations.
90 95 100 105 110 115 120 125 130 1350
5
10
15
20
25 RbZL2+
RbZL2PhCN'+
RbZL2MeCN+
Rela
tive
occu
panc
y / %
(COM+) / o
Figure S76. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for Rb+–Z–L2
complexes in benzonitrile obtained by MD simulations.
51
Table S18. Energies of interactions of E–L2 with lithium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC;
dref = 7,85 Å.a
LiE–L2+ LiE–L2PhCN'+ LiE–L2PhCN+ LiE–L2MeCN+
E(M+–L) / kJ mol–1 –488 –480 –490 –498E(L–PhCN) / kJ mol–1 –713 –732 –758 –716E(L–MeCNinkl) / kJ mol–1 – – – –52E(M+–PhCN) / kJ mol–1 –17 –44 –13 –20E(M+–MeCNinkl) / kJ mol–1 – – – 10tukupno / ns 50 23.5t / tukupno 0.711 0.166 0.123 1.00N(koordiniranih karbonila) 2.2 1.98 2.1 2.25N(PhCNinkl) – 3 8 –
/ Åd 6.828.56
7.768.39
7.538.57
7.897.86
|d – dref| / Å1.040.73
0.230.55
0.380.72
0.270.27
σ(d) / Å 0.540.39
0.270.27
0.360.30
0.330.33
Figure S77. Structures of a) LiE–L2PhCN'+ and b) LiE–L2PhCN+ obtained by MD simulations
in benzonitrile at 25 oC. Hydrogen atoms are omitted for clarity.
52
a) b)
1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.5 2.60
5
10
15
20
25
30
Rela
tive
occu
panc
y / %
d(OM+) / A
LiEL2+
LiEL2PhCN'+
LiEL2PhCN+
LiEL2MeCN+
o
Figure S78. Distribution of metal cation-carbonyl oxygen bond length for Li+–E–L2 complexes
in benzonitrile obtained by MD simulations.
95 100 105 110 115 120 125 130 135 140 145 1500
5
10
15
20
25 LiEL2+
LiEL2PhCN'+
LiEL2PhCN+
LiEL2MeCN+
Rela
tive
occu
panc
y / %
(COM+) / o
Figure S79. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for Li+–E–L2
complexes in benzonitrile obtained by MD simulations.
53
Table S19. Energies of interactions of E–L2 with sodium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC;
dref = 7,85 Å.a
NaE–L2+ NaE– L2PhCN'+ NaE– L2PhCN+ NaE– L2MeCN+
E(M+–L) / kJ mol–1 –432 –415 –437 –434E(L–PhCN) / kJ mol–1 –711 –734 –752 –712E(L–MeCNincl) / kJ mol–1 – – – –41E(M+–PhCN) / kJ mol–1 –14 –38 –11 –18E(M+–MeCNincl) / kJ mol–1 – – – –3ttotal / ns 50 15.5t / ttotal 0.940 0.052 0.014 1N(coordination) 3.61 3.02 3.79 3.61N(PhCNincl) – 17 1 –
/ Åd 7.687.76
7.948.13
7.968.08
7.867.81
|d – dref| / Å0.480.46
0.250.34
0.350.42
0.220.22
σ(d) / Å 0.590.58
0.300.31
0.410.44
0.280.27
Figure S80. Structures of a) NaE–L2PhCN'+ and b) NaE–L2PhCN+ obtained by MD simulations
in benzonitrile at 25 oC. Hydrogen atoms are omitted for clarity.
54
a) b)
2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.0 3.10
5
10
15
20
25
Rela
tive
occu
panc
y / %
d(OM+) / A
NaEL2+
NaEL2PhCN'+
NaEL2PhCN+
NaEL2MeCN+
o
Figure S81. Distribution of metal cation-carbonyl oxygen bond length for Na+–E–L2 complexes
in benzonitrile obtained by MD simulations.
90 95 100 105 110 115 120 125 130 1350
5
10
15
20
25
30
Rela
tive
occu
panc
y / %
NaEL2+
NaEL2PhCN'+
NaEL2PhCN+
NaEL2MeCN+
(COM+) / o
Figure S82. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for Na+–E–L2
complexes in benzonitrile obtained by MD simulations.
55
Table S20. Energies of interactions of E–L2 with potassium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC;
dref = 7,85 Å.a
KE–L2+ KE–L2PhCN'+ KE–L2PhCN+ KE–L2MeCN+
E(M+–L) / kJ mol–1 –344 –343 –344 –342E(L–PhCN) / kJ mol–1 –724 –762 –799 –721E(L–MeCNincl) / kJ mol–1 – – – –51E(M+–PhCN) / kJ mol–1 –10 –28 –8 –14E(M+–MeCNincl) / kJ mol–1 – – – 8ttotal / ns 25 50t / ttotal 0.990 0.005 0.005 1N(coordination) 3.90 3.82 3.92 3.93N(PhCNincl) – 1 4 –
/ Åd 7.607.74
7.977.98
7.988.03
7.797.78
|d – dref| / Å0.490.44
0.270.24
0.310.34
0.210.21
σ(d) / Å 0.570.55
0.300.26
0.370.37
0.260.26
Figure S83. Structures of a) KE–L2PhCN'+ and b) KE–L2PhCN+ obtained by MD simulations
in benzonitrile at 25 oC. Hydrogen atoms are omitted for clarity.
56
a) b)
2.4 2.5 2.6 2.7 2.8 2.9 3.0 3.10
5
10
15
20
25
30
Rela
tive
occu
panc
y / %
d(OM+) / A
KEL2+
KEL2PhCN'+
KEL2PhCN+
KEL2MeCN+
o
Figure S84. Distribution of metal cation-carbonyl oxygen bond length for K+–Z–L2 complexes
in benzonitrile obtained by MD simulations.
90 95 100 105 110 115 120 125 130 1350
5
10
15
20
25
Rela
tive
occu
panc
y / %
KEL2+
KEL2PhCN'+
KEL2PhCN+
KEL2MeCN+
(COM+) / o
Figure S85. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for K+–E–L2
complexes in benzonitrile obtained by MD simulations.
57
Table S21. Energies of interactions of E–L2 with rubidium cation, benzonitrile, and acetonitrile,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC;
dref = 7,85 Å.a
RbE–L2+ RbE– L2PhCN'+ RbE– L2PhCN+ RbE– L2MeCN+
E(M+–L) / kJ mol–1 –306 – –318 –306E(L–PhCN) / kJ mol–1 –707 – –787 –708E(L–MeCNincl) / kJ mol–1 – – – –51E(M+–PhCN) / kJ mol–1 –13 – –6 –12E(M+–MeCNincl) / kJ mol–1 – – – 7ttotal / ns 17.8 13.2t / ttotal 0.966 0 0.034 1N(coordination) 3.97 – 4.00 3.92N(PhCNincl) – – 1 –
/ Åd 7.507.79
– 7.748.21
7.777.75
|d – dref| / Å0.560.46
– 0.300.44
0.270.28
σ(d) / Å 0.610.58
– 0.360.34
0.220.23
Figure S86. Structure RbE–L2PhCN+ obtained by MD simulations in benzonitrile at 25 oC.
Hydrogen atoms are omitted for clarity.
58
2.5 2.6 2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.40
5
10
15
20
25
30
RbEL2+
RbEL2PhCN+
RbEL2MeCN+
Rela
tive
occu
panc
y / %
d(OM+) / Ao
Figure S87. Distribution of metal cation-carbonyl oxygen bond length for Rb+–E–L2 complexes
in benzonitrile obtained by MD simulations.
90 95 100 105 110 115 120 125 130 1350
5
10
15
20
25 RbEL2+
RbEL2PhCN+
RbEL2MeCN+
Rela
tive
occu
panc
y / %
(COM+) / o
Figure S88. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for Rb+–E–L2
complexes in benzonitrile obtained by MD simulations.
59
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
-3
-2
-1
0
1
2
E
-Z(R
elat
ive o
ccup
ancy
) / %
d(OM+) / A
LiL2MeCN+
NaL2MeCN+
KL2MeCN+
RbL2MeCN+
CsL2MeCN+
o
Figure S89. Difference in the distribution of metal cation-carbonyl oxygen bond length between
E–L2 and L2–Z complexes with Li+ cation in acetonitrile obtained by MD simulations.
90 95 100 105 110 115 120 125 130 135 140 145 150-6
-5
-4
-3
-2
-1
0
1
2
3
4
5
E-Z(R
elat
ive o
ccup
ancy
) / %
LiL2MeCN+
NaL2MeCN+
KL2MeCN+
RbL2MeCN+
CsL2MeCN+
(COM+) / o
Figure S90. Difference in the distribution of metal cation-carbonyl oxygen-carbonyl carbon
angle between E–L2 and L2–Z complexes with Li+ cation in acetonitrile obtained by MD
simulations.
60
Complexation of L1 in MeOH
20 40 60 80 100 12050
51
52
53
54
55
56
a)
P /
W
t / min0.0 0.4 0.8 1.2 1.6 2.0
-0.21
-0.18
-0.15
-0.12
-0.09
-0.06
-0.03
b)
(H
) / m
Jn(Li+) / n(L1)
Figure S91. a) Microcalorimetric titration of L1 (c = 4.05 10–4 mol dm–3, V = 1.4182 cm3) with
LiClO4 (c = 4.59 10–3 mol dm–3) in methanol; t = 25 °C; b) Dependence of successive enthalpy
change on n(Li+) / n(L1) ratio. ■ experimental; — calculated.
10 20 30 40 50 60 70 80 90 10025
30
35
40
45
50
55
a)
P /
W
t / min0 1 2 3 4 5
-1.4
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
b)
(H
) / m
J
n(Rb+) / n(L1)
Figure S92. a) Microcalorimetric titration of L1 (c = 2.36 10–3 mol dm–3, V = 1.4182 cm3) with
RbNO3 (c = 1.70 10–2 mol dm–3) in methanol; t = 25 °C; b) Dependence of successive enthalpy
change on n(Rb+) / n(L1) ratio. ■ experimental; — calculated.
61
20 40 60 80 100 120 140
35
40
45
50
55a)
P /
W
t / min0.0 0.4 0.8 1.2 1.6 2.0
-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0.0
b)
(H
) / m
J
n(K+) / n(LiL1+)
Figure S93. a) Microcalorimetric titration of LiL1+ (c = 2.69 10–4 mol dm–3, V = 1.4182 cm3)
with KClO4 (c = 2.72 10–3 mol dm–3) in methanol; t = 25 °C; b) Dependence of successive
enthalpy change on n(K+) / n(LiL1+) ratio. ■ experimental; — calculated.
20 40 60 80 10048
49
50
51
52
53
54
55
56
57
a)
P /
W
t / min0.0 0.4 0.8 1.2 1.6 2.0 2.4
-0.35
-0.30
-0.25
-0.20
-0.15
-0.10
-0.05
0.00
b)
(H
) / m
J
n(Na+) / n(KL1+)
Figure S94. a) Microcalorimetric titration of KL1+ (c = 3.96 10–4 mol dm–3, V = 1.4182 cm3)
with NaClO4 (c = 4.28 10–3 mol dm–3) in methanol; t = 25 °C; b) Dependence of successive
enthalpy change on n(Na+) / n(KL1+) ratio. ■ experimental; — calculated.
62
Table S22. Energies of interactions of L1 with lithium, sodium and potassium cations and
methanol, occurrence time ratio of different chemical species, and the number of carbonyl groups
which coordinate metal cation in the complexes obtained by MD simulations in benzonitrile at 25 oC; dref = 7,85 Å.a
Li+ Na+ K+
LiL1+ LiL1MeOH+ NaL1+ NaL1MeOH+ KL1+ KL1MeOH+
E(M+–L) / kJ mol–1 –514 –519 –450 –453 –347 –348E(L–MeOH) / kJ mol–1 –596 –650 –589 –643 –589 –637E(L–MeOHincl) / kJ mol–1 – –50 – –47 – –48E(M+–MeOH) / kJ mol–1 –12 –5 –9 –3 –8 –2E(M+–MeOHincl) / kJ mol–1 – 7 – 7 – 7ttotal / ns 50 50 50t / ttotal 0.059 0.941 0.020 0.980 0.025 0.975N(coordination) 2.28 2.52 3.46 3.65 3.96 3.98N(MeOHincl) – 21 – 12 – 8
/ Åd 7.567.92
7.877.93
7.607.91
7.837.87
7.657.75
7.807.81
|d – dref| / Å0.680.73
0.240.25
0.360.43
0.210.21
0.400.43
0.210.21
σ(d) / Å 0.800.82
0.300.30
0.460.49
0.260.26
0.510.51
0.250.26
63
Figure S95. Structures of a) LiL1MeOH+, b) NaL1MeOH+ and c) KL1MeOH+ obtained by MD
simulations in methanol at 25 oC. Hydrogen atoms are omitted for clarity.
64
a) b)
c)
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.40
5
10
15
20
25
30
Rela
tive
occu
panc
y / %
LiL1MeOH+
NaL1MeOH+
KL1MeOH+
d(OM+) / Ao
Figure S96. Distribution of metal cation-carbonyl oxygen bond length for M+–L1 complexes in
methanol obtained by MD simulations.
90 95 100 105 110 115 120 125 130 135 140 145 150 1550
5
10
15
20
25
Rela
tive
occu
panc
y / %
LiL1MeOH+
NaL1MeOH+
KL1MeOH+
(COM+) / o
Figure S97. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for M+–L1
complexes in methanol obtained by MD simulations.
65
Complexation of L2 in MeOH
20 30 40 50 60 70 80 90 100 110
39
42
45
48
51
54
57
a)
P /
W
t / min0.0 0.4 0.8 1.2 1.6 2.0 2.4
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
b)
(H
) / m
Jn(Li+) / n(L2)
Figure S98. a) Microcalorimetric titration of L2 (c = 6.73 10–4 mol dm–3, V = 1.4182 cm3) with
LiClO4 (c = 7.76 10–3 mol dm–3) in methanol; t = 25 °C; b) Dependence of successive enthalpy
change on n(Li+) / n(L2) ratio. ■ experimental; — calculated.
10 20 30 40 50 60 70 80 90 100
15
20
25
30
35
40
45
50
55
60
a)
P /
W
t / min0.0 0.5 1.0 1.5 2.0
-2.0
-1.6
-1.2
-0.8
-0.4
0.0
b)
(H
) / m
J
n(K+) / n(L2)
Figure S99. a) Microcalorimetric titration of L2 (c = 3.35 10–4 mol dm–3, V = 1.4182 cm3) with
KClO4 (c = 3.15 10–3 mol dm–3) in methanol; t = 25 °C; b) Dependence of successive enthalpy
change on n(K+) / n(L2) ratio. ■ experimental; — calculated.
66
10 20 30 40 50 60 70 80 90 10040
42
44
46
48
50
52
54
56
58
a)
P /
W
t / min0 1 2 3 4
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
b)
(H
) / m
J
n(Rb+) / n(L2)
Figure S100. a) Microcalorimetric titration of L2 (c = 3.35 10–4 mol dm–3, V = 1.4182 cm3)
with RbNO3 (c = 5.74 10–3 mol dm–3) in methanol; t = 25 °C; b) Dependence of successive
enthalpy change on n(Rb+) / n(L2) ratio. ■ experimental; — calculated.
10 20 30 40 50 60 70 80 9050
51
52
53
54
55
56
57
58
a)
P /
W
t / min0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75
-0.25
-0.20
-0.15
-0.10
-0.05
0.00
b)
(H
) / m
J
n(Na+) / n(KL2+)
Figure S101. a) Microcalorimetric titration of KL2+ (c = 3.07 10–4 mol dm–3, V = 1.4182 cm3)
with NaClO4 (c = 3.86 10–3 mol dm–3) in methanol; t = 25 °C; b) Dependence of successive
enthalpy change on n(Na+) / n(KL2+) ratio. ■ experimental; — calculated.
67
Table S23. Energies of interactions of Z–L2 with lithium and sodium cations and methanol,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in methanol at 25 oC; dref =
7,85 Å.a
Li+ Na+
LiZ–L2+ LiZ–L2MeOH+ NaZ–L2+ NaZ–L2MeOH+
E(M+–L) / kJ mol–1 –510 –509 –439 –444E(L–MeOH) / kJ mol–1 –503 –571 –503 –557E(L–MeOHincl) / kJ mol–1 – –50 – –48E(M+–MeOH) / kJ mol–1 –15 –11 –13 –7E(M+–MeOHincl) / kJ mol–1 – 8 – 7ttotal / ns 50 50t / ttotal 0.033 0.967 0.019 0.981N(coordination) 2.33 2.61 3.82 3.93N(MeOHincl) – 12 – 10
/ Åd 7.727.78
7.867.93
7.697.81
7.847.86
|d – dref| / Å0.690.70
0.240.25
0.380.42
0.210.21
σ(d) / Å 0.810.82
0.300.30
0.490.51
0.260.26
Figure S102. Structures of a) LiZ–L2MeOH+ and b) NaZ–L2MeOH+ obtained by MD
simulations in methanol at 25 oC. Hydrogen atoms are omitted for clarity.
68
a) b)
Table S24. Energies of interactions of Z–L2 with potassium and rubidium cations and methanol,
occurrence time ratio of different chemical species, and the number of carbonyl groups which
coordinate metal cation in the complexes obtained by MD simulations in methanol at 25 oC; dref =
7,85 Å.a
K+ Rb+
KZ–L2+ KZ–L2MeOH+ RbZ–L2+ RbZ–L2MeOH+
E(M+–L) / kJ mol–1 –391 –341 –305 –305E(L–MeOH) / kJ mol–1 –504 –559 –503 –557E(L–MeOHincl) / kJ mol–1 – –50 – –48E(M+–MeOH) / kJ mol–1 –10 –5 –8 –3E(M+–MeOHincl) / kJ mol–1 – 7 – 7ttotal / ns 50 50t / ttotal 0.022 0.978 0.048 0.952N(coordination) 3.94 3.96 3.94 3.93N(MeOHincl) – 8 – 9
/ Åd 7.697.74
7.817.82
7.597.75
7.787.79
|d – dref| / Å0.400.41
0.210.21
0.480.43
0.210.21
σ(d) / Å 0.490.50
0.260.26
0.560.54
0.260.25
Figure S103. Structures of a) KZ–L2MeOH+ and b) RbZ–L2MeOH+ obtained by MD
simulations in methanol at 25 oC. Hydrogen atoms are omitted for clarity.
69
a) b)
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.40
5
10
15
20
25
30 LiZL2MeOH+
NaZL2MeOH+
KZL2MeOH+
RbZL2MeOH+
Rela
tive
occu
panc
y / %
d(OM+) / Ao
Figure S104. Distribution of metal cation-carbonyl oxygen bond length for M+–Z–L2 complexes
in methanol obtained by MD simulations.
90 95 100 105 110 115 120 125 130 135 140 145 150 1550
5
10
15
20
25
30 LiZL2MeOH+
NaZL2MeOH+
KZL2MeOH+
RbZL2MeOH+
Rela
tive
occu
panc
y / %
(COM+) / o
Figure S105. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for M+–Z–L2
complexes in methanol obtained by MD simulations.
70
Table S25. Energies of interactions of E–L2 with lithium, sodium and potassium cations and
methanol, occurrence time ratio of different chemical species, and the number of carbonyl groups
which coordinate metal cation in the complexes obtained by MD simulations in methanol at 25 oC;
dref = 7,85 Å.a
Li+ Na+
LiE–L2+ LiE–L2MeOH+ NaE–L2+ NaE–L2MeOH+
E(M+–L) / kJ mol–1 –493 –500 –430 –439E(L–MeOH) / kJ mol–1 –530 –696 –546 –599E(L–MeOHincl) / kJ mol–1 – –50 – –49E(M+–MeOH) / kJ mol–1 –12 –8 –9 –2E(M+–MeOHincl) / kJ mol–1 – 8 – 7ttotal / ns 50 50t / ttotal 0.058 0.942 0.015 0.985N(coordination) 2.13 2.34 3.03 3.42N(MeOHincl) – 16 – 11
/ Åd 7.747.70
7.877.92
7.857.64
7.847.86
|d – dref| / Å0.800.82
0.260.27
0.430.48
0.210.21
σ(d) / Å 0.900.94
0.320.32
0.550.60
0.260.26
Figure S106. Structures of a) LiE–L2MeOH+ and b) NaE–L2MeOH+ obtained by MD
simulations in methanol at 25 oC. Hydrogen atoms are omitted for clarity.
71
a) b)
Table S26. Energies of interactions of E–L2 with lithium, sodium and potassium cations and
methanol, occurrence time ratio of different chemical species, and the number of carbonyl groups
which coordinate metal cation in the complexes obtained by MD simulations in methanol at 25 oC;
dref = 7,85 Å.a
K+ Rb+
KE–L2+ KE–L2MeOH+ RbE–L2+ RbE–L2MeOH+
E(M+–L) / kJ mol–1 –343 –344 –308 –306E(L–MeOH) / kJ mol–1 –530 –599 –531 –584E(L–MeOHincl) / kJ mol–1 – –48 – –49E(M+–MeOH) / kJ mol–1 –3 2 –2 1E(M+–MeOHincl) / kJ mol–1 – 6 – 7ttotal / ns 50 50t / ttotal 0.026 0.974 0.075 0.925N(coordination) 3.90 3.91 3.94 3.96N(MeOHincl) – 8 – 9
/ Åd 7.567.82
7.797.81
7.577.75
7.787.78
|d – dref| / Å0.450.37
0.210.21
0.490.44
0.210.21
σ(d) / Å 0.510.48
0.250.25
0.570.55
0.250.25
Figure S107. Structures of a) KE–L2MeOH+ and b) RbE–L2MeOH+ obtained by MD
simulations in methanol at 25 oC. Hydrogen atoms are omitted for clarity.
72
a) b)
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.40
5
10
15
20
25
30 LiZL2MeOH+
NaZL2MeOH+
KZL2MeOH+
RbZL2MeOH+
Rela
tive
occu
panc
y / %
d(OM+) / Ao
Figure S108. Distribution of metal cation-carbonyl oxygen bond length for M+–Z–L2 complexes
in methanol obtained by MD simulations.
90 95 100 105 110 115 120 125 130 135 140 145 150 1550
5
10
15
20
25 LiZL2MeOH+
NaZL2MeOH+
KZL2MeOH+
RbZL2MeOH+
Rela
tive
occu
panc
y / %
(COM+) / o
Figure S109. Distribution of metal cation-carbonyl oxygen-carbonyl carbon angle for M+–Z–L2
complexes in methanol obtained by MD simulations.
73
K+(MeCN) + L1(MeCN) KL1+(MeCN)
K+(MeOH) + L1(MeOH) KL1+(MeOH)
ΔrG° = –33.4 kJ mol–1
ΔrG° = –52.5 kJ mol–1
ΔtG° = 2.1 kJ mol–1 ΔtG° = 9.5 kJ mol–1 ΔtG° = –7.5 kJ mol–1
Rb+(MeCN) + L1(MeCN) RbL1+(MeCN)
Rb+(MeOH) + L1(MeOH) RbL1+(MeOH)
ΔrG° = –21.7 kJ mol–1
ΔtG° = 4 kJ mol–1 ΔtG° = 11.3 kJ mol–1 ΔtG° = –7.5 kJ mol–1
Cs+(MeCN) + L1(MeCN) CsL1+(MeCN)
Cs+(MeOH) + L1(MeOH) CsL1+(MeOH)
ΔrG° = –8.5 kJ mol–1
ΔtG° = 3 kJ mol–1 ΔtG° = 8.6 kJ mol–1 ΔtG° = –7.5 kJ mol–1
Scheme S2. Thermodynamic cycles for complexation of a) K+, b) Rb+ and c) Cs+ with L1 in
acetonitrile and methanol expressed in terms of Gibbs energies.
74
a)
b)
c)
ΔrG° = –63.3 kJ mol–1
Li+(MeCN) + L2(MeCN) LiL2+(MeCN)
Li+(MeOH) + L2(MeOH) LiL2+(MeOH)
ΔrG° = –20.72 kJ mol–1
ΔtG° = –21 kJ mol–1 ΔtG° = 9.6 kJ mol–1 ΔtG° = –11 kJ mol–1
ΔrG° = –70.0 kJ mol–1
Na+(MeCN) + L2(MeCN) NaL2+(MeCN)
Na+(MeOH) + L2(MeOH) NaL2+(MeOH)
ΔrG° = –41.9 kJ mol–1
ΔtG° = –5.4 kJ mol–1 ΔtG° = 11.7 kJ mol–1 ΔtG° = –11 kJ mol–1
ΔrG° = –48.2 kJ mol–1
K+(MeCN) + L2(MeCN) KL2+(MeCN)
K+(MeOH) + L2(MeOH) KL2+(MeOH)
ΔrG° = –30.45 kJ mol–1
ΔtG° = 2.1 kJ mol–1 ΔtG° = 8.9 kJ mol–1 ΔtG° = –11 kJ mol–1
75
a)
b)
c)
ΔrG° = –32.0 kJ mol–1
Rb+(MeCN) + L2(MeCN) RbL2+(MeCN)
Rb+(MeOH) + L2(MeOH) RbL2+(MeOH)
ΔrG° = –18.36 kJ mol–1
ΔtG° = 4 kJ mol–1 ΔtG° = 6.6 kJ mol–1 ΔtG° = –11 kJ mol–1
Scheme S3. Thermodynamic cycles for complexation of a) Li+, b) Na+, c) K+ and d) Rb+ with L2
in acetonitrile and methanol expressed in terms of Gibbs energies.
76
d)