neutral glycoconjugated amide-based calix[4]arenes: … · 2017. 12. 13. · nikola cindro, aajosip...
TRANSCRIPT
-
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
P3 1H NMR (400 MHz, CDCl3)
P3 13C NMR (101 MHz, CDCl3)
-
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
P5 1H NMR (400 MHz, CDCl3)
P5 13C NMR (101 MHz, CDCl3)
-
S6
P6 1H NMR (400 MHz, CDCl3)
P6 13C NMR (101 MHz, CDCl3)
-
S7
P7 1H NMR (400 MHz, CDCl3)
P7 13C NMR (101 MHz, CDCl3)
-
S8
L2 1H NMR (400 MHz, MeOD)
L2 13C NMR (101 MHz, MeOD)
-
S9
P9 1H NMR (400 MHz, CDCl3)
P9 13C NMR (101 MHz, CDCl3)
-
S10
P10 1H NMR (400 MHz, CDCl3)
P10 13C NMR (101 MHz, CDCl3)
-
S11
L3 1H NMR (400 MHz, MeOD)
L3 13C NMR (101 MHz, MeOD)
-
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 ×
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(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)
Figure S12. a) Spectrophotometric titration of L1 (c = 2.80 × 10−4 mol dm−3) with LiClO4 (c = 3.00 ×
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(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
Figure S14. a) Spectrophotometric titration of L1 (c = 2.81 × 10−4 mol dm−3) with RbCl (c = 5.00 × 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. 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
Figure S15. a) Spectrophotometric titration of L1 (c = 2.81 × 10−4 mol dm−3) with CsCl (c = 5.00 × 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. The
n(CsCl) / n(L1) molar ratio at the end of titration is 1330.
-
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 ×
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(NaClO4) / n(L2) molar ratio. ■ experimental, ─ calculated.
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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
Figure S19. a) Spectrophotometric titration of L2 (c = 3.03 × 10−4 mol dm−3) with RbCl (c = 3.05 × 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(RbCl) / n(L2) molar ratio at the end of titration is 75.
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S22
265 280 295
0.0
0.3
0.6
0.9
A
/ nm
Figure S20. a) Spectrophotometric titration of L2 (c = 3.03 × 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(L2) molar ratio at the end of titration is 160.
265 280 295
0.0
0.3
0.6
0.9
1.2
/ nm
A
Figure S21. a) Spectrophotometric titration of L2 (c = 3.96 × 10−4 mol dm−3) with LiClO4 (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(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.
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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)
Figure S26. a) Spectrophotometric titration of L3 (c = 2.48 × 10−4 mol dm−3) with LiClO4 (c = 3.01 ×
10−3 mol dm−3) in methanol 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.
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 ×
10−3 mol dm−3) in methanol 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(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)
Figure S29. a) Spectrophotometric titration of L3 (c = 2.60 × 10−4 mol dm−3) with RbCl (c = 3.05 × 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(L3) molar ratio. ■ experimental, ─ calculated.
-
S27
255 275 295
0.0
0.3
0.6
0.9
A
/ nm
Figure S30. a) Spectrophotometric titration of L3 (c = 2.48 × 10−4 mol dm−3) with CsCl (c = 7.10 × 10−2
mol dm−3) in methanol at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.4 ml. Spectrum is corrected for dilution. The
n(CsCl) / n(L3) molar ratio upon addition of titrant is 119.
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)
Figure S31. a) Spectrophotometric titration of L3 (c = 2.66 × 10−4 mol dm−3) with LiClO4 (c = 1.60 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(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
Figure S35. a) Spectrophotometric titration of L3 (c = 2.80 × 10−4 mol dm−3) with CsCl (c = 2.64 × 10−1
mol dm−) in water at (25.0 ± 0.1) °C; l = 1 cm, V0 = 2.5 ml. Spectrum is corrected for dilution. The
n(CsCl) / n(L3) molar ratio upon addition of titrant is 943.
-
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)
Figure S37. Microcalorimetric titration of L3 (c = 2.85 × 10–4 mol dm–3) with NaClO4 (c = 2.06 × 10–2
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)
Figure S38. Microcalorimetric titration of L3 (c = 1.21 × 10–4 mol dm–3) with NaClO4 (c = 1.12 × 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(L3) molar ratio. The values have been corrected for titrant dilution enthalpy. ■-
experimental, – calculated.
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
mol dm–3) in methanol at 25. 0 °C; V = 1.4182 ml. b) Dependence of successive enthalpy changes on
n(NaClO4) / n(P3) molar ratio. The values have been corrected for titrant dilution enthalpy. ■
experimental, – calculated.
-
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)