Neutral Glycoconjugated Amide-Based Calix[4]arenes: … · 2017. 12. 13. · Nikola Cindro, aaJosip...

Neutral Glycoconjugated Amide-Based Calix[4]arenes:

Complexation of Alkali Metal Cations in Water

Nikola Cindro,a Josip Požar,a Dajana Barišić,a Nikola Bregović,a Katarina Pičuljan,a Renato

Tomaš,b Leo Frkanec,c Vladislav Tomišić*a

a

b

c

ELECTRONIC SUPPLEMENTARY INFORMATION

Table of Contents

1. NMR Spectra of New Compounds ...................................................................................................................... 2

2. Spectrophotometric Titration Data .................................................................................................................... 16

3. Microcalorimetric Titration Data ...................................................................................................................... 30

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2017

S2

1. NMR Spectra of New Compounds

P2 1H NMR (400 MHz, CDCl3)

P2 13C NMR (101 MHz, CDCl3)

S3



S4

L1 1H NMR (400 MHz, MeOD)

L1 13C NMR (101 MHz, MeOD)

Doubling of t-butyl signal, CH aromatic

and CH3CN signals is a result of Na+

presence in deuterated solvents which

leads to some degree of complex

formation. This was confirmed by ICP

analysis of solvents used.

S5



S6



S7



S8



S9



S10



S11



S12

Figure S1. Concentration dependence of 1H NMR spectra of L1 in D2O at 25 ºC.

Figure S2. Concentration dependence of 1H NMR spectra of NaL1+ in D2O at 25 ºC.

c / mol dm−3

10−4

10−3

10−2

c / mol dm−3

10−4

10−3

10−2

S13

Figure S3. NOESY NMR spectrum of L1 in D2O at 25 ºC.

Figure S4. NOESY NMR spectrum of NaL1+ in D2O at 25 ºC.

S14

Figure S5. Temperature dependence of 1H NMR spectra of L1 in D2O.

Figure S6. Temperature dependence of 1H NMR spectra of NaL1+ in D2O.

t / ºC

25

80

t / ºC

25

80

S15

Figure S7. Temperature dependence 1H NMR spectra of P3 in MeOD.

t / ºC

25

50

S16

2. Spectrophotometric Titration Data

L1

250 260 270 280 290 300

0.0

0.2

0.4

0.6

0.8

1.0

A

/ nm

(a)

0 5 10 15

0.7

0.8

0.9A

n(LiClO4) / n(L1)

(b)

Figure S8. a) Spectrophotometric titration of L1 (c = 2.53 × 10−4 mol dm−3) with LiClO4 (c = 5.18 ×

10−3 mol dm−3) in methanol at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution.

b) Dependence of absorbance at 280 nm on n(LiClO4) / n(L1) molar ratio. ■ experimental, ─ calculated.

255 275 295

0.0

0.2

0.4

0.6

0.8

1.0

A

/ nm

(a)

0 1 2 3

0.7

0.8

0.9A

n(KClO4) / n(L1)

(b)

Figure S9. a) Spectrophotometric titration of L1 (c = 2.56 × 10−4 mol dm−3) with KClO4 (c = 1.46 ×


b) Dependence of absorbance at 280 nm on n(KClO4) / n(L1) molar ratio. ■ experimental, ─ calculated.

S17

255 283

0.0

0.3

0.6

0.9A

/ nm

(a)

0 25 50 75 100

0.7

0.8

0.9A

n(RbCl) / n(L1)

(b)

Figure S10. a) Spectrophotometric titration of L1 (c = 2.52 × 10−4 mol dm−3) with RbCl (c = 3.10 × 10−2

mol dm−3) in methanol at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. b)

Dependence of absorbance at 280 nm on n(RbCl) / n(L1) molar ratio. ■ experimental, ─ calculated.

265 285 305

0.0

0.3

0.6

0.9A

/ nm

Figure S11. a) Spectrophotometric titration of L1 (c = 2.52 × 10−4 mol dm−3) with CsCl (c = 7.78 × 10−2

mol dm−3) in methanol at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. The

n(CsCl) / n(L1) molar ratio at the end of titration is 216.

S18

260 280 300

0.0

0.2

0.4

0.6

0.8

1.0A

/ nm

(a)

0 200 400 600

0.7

0.8

0.9

1.0

A

n(LiClO4) / n(L1)

(b)


10−1 mol dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. b)

Dependence of absorbance at 280 nm on n(LiClO4) / n(L1) molar ratio. ■ experimental, ─ calculated.

255 275 295

0.0

0.3

0.6

0.9A

/ nm

(a)

0 100 200

0.7

0.8

0.9A

n(KCl) / n(L1)

(b)

Figure S13. a) Spectrophotometric titration of L1 (c = 2.80 × 10−4 mol dm−3) with KCl (c = 1.00 × 10−1

mol dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. b)

Dependence of absorbance at 280 nm on n(KCl) / n(L1) molar ratio. ■ experimental, ─ calculated.

S19

255 275 295

0.0

0.3

0.6

0.9A

/ nm


mol dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. The

n(RbCl) / n(L1) molar ratio at the end of titration is 1332.

255 275 295

0.0

0.3

0.6

0.9A

/ nm


mol dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. The


S20

L2

265 280 295

0.0

0.3

0.6

0.9

A

/ nm

Figure S16. a) Spectrophotometric titration of L2 (c = 3.04 × 10−4 mol dm−3) with LiClO4 (c = 1.00 mol

dm−3) in methanol at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. The

n(LiClO4) / n(L2) molar ratio at the end of titration is 2467.

265 280 295

0.0

0.3

0.6

0.9

A

/ nm

(a)

0 10 20

0.68

0.72

0.76

n(NaClO4) / n(L2)

A

(b)

Figure S17. a) Spectrophotometric titration of L2 (c = 3.04 × 10−4 mol dm−3) with NaClO4 (c = 9.94 ×


b) Dependence of absorbance at 280 nm on n(NaClO4) / n(L2) molar ratio. ■ experimental, ─ calculated.

S21

265 280 295

0.0

0.3

0.6

0.9

/ nm

A

(a)

0 200 400 600

0.54

0.60

0.66

A

n(KSCN) / n(L2)

(b)

Figure S18. a) Spectrophotometric titration of L2 (c = 3.04 × 10−4 mol dm−3) with KSCN (c = 3.00 ×

10−1 mol dm−3) in methanol at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution

and the absorption of KSCN. b) Dependence of absorbance at 285 nm on n(KSCN) / n(L2) molar ratio.

■ experimental, ─ calculated.

265 280 295

0.0

0.3

0.6

0.9

A

/ nm



n(RbCl) / n(L2) molar ratio at the end of titration is 75.

S22

265 280 295

0.0

0.3

0.6

0.9

A

/ nm




265 280 295

0.0

0.3

0.6

0.9

1.2

/ nm

A


dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.2 ml. Spectra are corrected for dilution. The n(LiClO4)

/ n(L2) molar ratio at the end of titration is 1152.

S23

265 280 295

0.0

0.3

0.6

0.9

/ nm

A

(a)

0 3000 6000 9000

0.72

0.78

0.84A

n(NaClO4) / n(L2)

(b)

Figure S22. a) Spectrophotometric titration of L2 (c = 3.03 × 10−4 mol dm−3) with NaClO4 (c = 4.03

mol dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. b)

Dependence of absorbance at 280 nm on n(NaClO4) / n(L2) molar ratio. ■ experimental, ─ calculated.

265 280 295

0.0

0.4

0.8

1.2

A

/ nm

Figure S23. a) Spectrophotometric titration of L2 (c = 3.96 × 10−4 mol dm−3) with KCl (c = 1.00 mol

dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.2 ml. Spectra are corrected for dilution. The n(KCl) /

n(L2) molar ratio at the end of titration is 1148.

S24

265 280 295

0.0

0.3

0.6

0.9

A

/ nm

Figure S24. a) Spectrophotometric titration of L2 (c = 2.99 × 10−4 mol dm−3) with RbCl (c = 1.67 × 10–

1 mol dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. The

n(RbCl) / n(L2) molar ratio upon addition of titrant is 418.

265 280 295

0.0

0.3

0.6

0.9

A

/ nm

Figure S25. a) Spectrophotometric titration of L2 (c = 2.99 × 10−4 mol dm−3) with CsCl (c = 1.67 × 10–

1 mol dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. The

n(CsCl) / n(L2) molar ratio upon addition of titrant is 418.

S25

L3

255 275 295

0.0

0.3

0.6

0.9A

/ nm

(a)

0 3 6

0.82

0.85

0.88

0.91

0.94

A

n(LiClO4) / n(L3)

(b)



b) Dependence of absorbance at 280 nm on n(LiClO4) / n(L3) molar ratio. ■ experimental, ─ calculated.

255 275 295

0.0

0.3

0.6

0.9A

/ nm

(a)

0 1 2

0.57

0.59

0.61

0.63

0.65

A

n(NaSCN) / n(L3K+)

(b)

Figure S27. a) Spectrophotometric titration of KL3+ (c = 2.40 × 10−4 mol dm−3) with NaSCN (c = 1.02

× 10−3 mol dm−3) in methanol at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution.

b) Dependence of absorbance at 270 nm on n(NaSCN) / n(KL3+) molar ratio. ■ experimental, ─

calculated.

S26

255 275 295

0.0

0.3

0.6

0.9

A

/ nm

(a)

0 1 2

0.80

0.86

0.92

A

n(KClO4) / n(L3)

(b)

Figure S28. a) Spectrophotometric titration of L3 (c = 2.48 × 10−4 mol dm−3) with KClO4 (c = 2.96 ×


b) Dependence of absorbance at 280 nm on n(KClO4) / n(L3) molar ratio. ■ experimental, ─ calculated.

255 275 295

0.0

0.3

0.6

0.9

A

/ nm

(a)

0 35 70

0.91

0.94

0.97A

n(RbCl) / n(L3)

(b)


mol dm−3) in methanol at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. b)

Dependence of absorbance at 280 nm on n(RbCl) / n(L3) molar ratio. ■ experimental, ─ calculated.

S27

255 275 295

0.0

0.3

0.6

0.9

A

/ nm


mol dm−3) in methanol at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.4 ml. Spectrum is corrected for dilution. The


255 275 295

0.0

0.3

0.6

0.9

A

/ nm

(a)

0 750 1500 2250

0.66

0.72

0.78

0.84A

n(LiClO4) / n(L3)

(b)


dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.2 ml. Spectra are corrected for dilution. b) Dependence

of absorbance at 280 nm on n(LiClO4) / n(L3) molar ratio. ■ experimental, ─ calculated.

S28

255 275 295

0.0

0.3

0.6

0.9

/ nm

A

(a)

0 5 10 15

0.70

0.75

0.80

0.85

A

n(NaClO4) / n(L3)

(b)

Figure S32. a) Spectrophotometric titration of L3 (c = 2.80 × 10−4 mol dm−3) with NaClO4 (c = 3.00 ×

10−2 mol dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.2 ml. Spectra are corrected for dilution. b)

Dependence of absorbance at 280 nm on n(NaClO4) / n(L3) molar ratio. ■ experimental, ─ calculated.

255 275 295

0.0

0.3

0.6

0.9

1.2

A

/ nm

(a)

0 2000 4000 6000

0.76

0.80

0.84

A

n(KCl) / n(L3)

(b)

Figure S33. a) Spectrophotometric titration of L3 (c = 2.71 × 10−4 mol dm−3) with KCl (c = 3.00 mol

dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.0 ml. Spectra are corrected for dilution. b) Dependence

of absorbance at 280 nm on n(KCl) / n(L3) molar ratio. ■ experimental, ─ calculated.

S29

255 275 295

0.0

0.3

0.6

0.9

A

/ nm

Figure S34. a) Spectrophotometric titration of L3 (c = 2.80 × 10−4 mol dm−3) with RbCl (c = 3.00 mol

dm−3) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.2 ml. Spectrum is corrected for dilution. The n(RbCl)

/ n(L3) molar ratio upon addition of titrant is 5357.

255 275 295

0.0

0.3

0.6

0.9

A

/ nm


mol dm−) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.5 ml. Spectrum is corrected for dilution. The


S30

3. Microcalorimetric Titration Data

0 20 40 60 80 100

0

2

4

6

8

10

12

14

P /

W

t / min

(a)

0.0 0.5 1.0 1.5 2.0 2.5-3.0

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

(

H)

/ m

J

n(Na+) / n(L1)

(b)

Figure S36. Microcalorimetric titration of L1 (c = 2.51 × 10–4 mol dm–3) with NaClO4 (c = 3.00 × 10–3

mol dm–3) in methanol at 25. 0 °C; V = 1.4182 ml. b) Dependence of successive enthalpy changes on

n(NaClO4) / n(L1) molar ratio. The values have been corrected for titrant dilution enthalpy.

0 20 40 60 80 100 12012

14

16

18

20

P /

W

t / min

(a)

0 5 10 15

-1.6

-1.4

-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

0.0

(

H)

/ m

J

n(Na+) / n(L3)

(b)


mol dm–3) in water at 25. 0 °C; V = 1.4182 ml. b) Dependence of successive enthalpy changes on

n(NaClO4) / n(L3) molar ratio. The values have been corrected for titrant dilution enthalpy. ■-

experimental, – calculated.

S31

0 30 60 90 120 150 180

9

10

11

12

P /

W

t / min

(a)

0.0 0.5 1.0 1.5 2.0

-0.4

-0.2

0.0

(

H)

/ m

J

n(Na+) / n(L3)

(b)



n(NaClO4) / n(L3) molar ratio. The values have been corrected for titrant dilution enthalpy. ■-


0 50 100 150 200 250 300

8

9

10

11

P/

mW

t / min

(a)

0.0 0.5 1.0 1.5 2.0

-0.6

-0.4

-0.2

0.0

(

H)

/ m

J

n(Na+) / n(P3)

(b)

Figure S39. Microcalorimetric titration of P3 (c = 1.83 × 10–4 mol dm–3) with NaClO4 (c = 1.87 × 10–3


n(NaClO4) / n(P3) molar ratio. The values have been corrected for titrant dilution enthalpy. ■


S32

Table S1. Thermodynamic parameters for complexation of sodium cation with L1 in water at 25 °C

obtained microcalorimetrically by using different sodium salts.a

a uncertainties of the last digit are given in parentheses as standard errors of the mean (N = 3)

Salt used log K rG°/ kJ mol–1 rH°/ kJ mol

–1 rS°/ J K–1 mol–1

NaClO4 4.95(2) –28.23(9) –58.6(8) –102(3)

NaCl 4.891(2) –27.92(1) –59.62(2) –106(1)

NaBr 4.916(5) –28.06(3) –57.2(2) –97.5(4)

NaI 4.872(9) –27.81(5) –56.2(2) –95.3(9)

NaSCN 4.897(4) –27.95(2) –55.8(2) –93.3(8)

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Neutral Glycoconjugated Amide-Based Calix[4]arenes: … · 2017. 12. 13. · Nikola Cindro, aaJosip...

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