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: ghorvat@chem.pmf.hr, vtomisic@chem.pmf.hr)

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)