The Syn and Anti isomers of the Porphyrinogen-like Precursor of … · 2013. 3. 12. · S5 4000.0...

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The Syn and Anti isomers of the Porphyrinogen-like Precursor of Calix[4]phyrin: Isolation, X-ray Structure, Anion Binding and Fluoride-ion-Mediated Proton-Deuterium Exchange Studies

Tapas Guchhait, Vikesh Kumar Jha and Ganesan Mani*

Department of Chemistry, Indian Institute of Technology, Kharagpur, India 721 302 Email: [email protected]

Contents

1. Experimental section

2. NMR and IR spectra

3. X-ray crystallography

4. UV-vis spectrum of calix[4]phyrin

5. NMR titrations and determination of binding constants

6. H/D Exchange

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013

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1. Experimental section

General

Solvents were purchased from commercial sources and distilled before use by following standard

procedures.

2. NMR and IR spectra

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0ppm

1.481.48

2.25

0.450.971.00

0.510.570.50

0.94

0.49

0.534

0.552

0.571

0.699

0.718

0.736

1.813

1.832

1.851

1.869

5.327

5.584

5.591

5.599

5.918

5.926

5.933

7.137

7.150

7.157

7.169

7.247

7.262

7.268

7.609

7.614

7.628

7.632

7.647

7.652

8.095

8.538

8.551

Figure S1. 1H NMR (400 MHz) spectrum of syn-dipyridyldihydrotetraethylcalix[4]pyrrole

isomer 2a in CDCl3.


S3

0102030405060708090100110120130140150160ppm

8.318

8.402

28.458

29.335

43.290

45.832

76.916

77.233

77.550

105.577

105.910

121.979

123.574

131.069

136.847

136.935

149.442

161.007

Figure S2. 13C{1H} NMR (100.6 MHz) spectrum of syn-

dipyridyldihydrotetraethylcalix[4]pyrrole isomer 2a in CDCl3.


S4

0102030405060708090100110120130140150160ppm

Figure S3. DEPT-135{1H} (100.6 MHz) NMR spectrum of syn-

dipyridyldihydrotetraethylcalix[4]pyrrole isomer 2a in CDCl3.


S5

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0

48.6

50

52

54

56

58

60

62

64

66

68

70

72

74

76

78

80

82

cm-1

%T

3517.77

3432.09

3297.67

2962.30

2930.80

2873.55

1589.81

1467.86

1434.49

1328.42

1280.70

1185.25

1095.53

1046.90

1001.12

926.25

774.99

755.23

701.33

529.761633.56

3226.89

Figure S4. IR spectrum of syn-dipyridyldihydrotetraethylcalix[4]pyrrole isomer 2a recorded as a

KBr disc.


S6

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0ppm

3.04

2.15

0.491.001.00

0.97

0.51

0.96

0.49

0.633

0.651

0.669

1.768

1.785

1.802

1.820

1.831

1.838

1.851

1.869

1.886

1.903

5.389

5.607

5.614

5.621

5.941

5.948

5.956

7.143

7.152

7.163

7.262

7.610

7.626

7.629

7.996

8.519

8.529

8.534

Figure S5. 1H NMR (400 MHz) spectrum of anti-dipyridyldihydrotetraethylcalix[4]pyrrole

isomer 2b in CDCl3.


S7

0102030405060708090100110120130140150160170ppm

8.462

29.246

43.408

46.011

76.915

77.232

77.549

105.953

105.988

121.932

123.261

131.062

136.765

137.065

149.279

161.599

Figure S6. 13C{1H} NMR (100.6 MHz) spectrum of anti-

dipyridyldihydrotetraethylcalix[4]pyrrole isomer 2b in CDCl3.


S8

0102030405060708090100110120130140150160ppm

Figure S7. DEPT-135{1H} NMR (100.6 MHz) spectrum of anti-

dipyridyldihydrotetraethylcalix[4]pyrrole isomer 2b in CDCl3.


S9

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0

35.0

40

45

50

55

60

65

70

75

80.8

cm-1

%T

3838.31

3750.473674.60

3574.67

3417.77

3310.03

3102.11

2964.53

2931.43

2873.15

1590.931572.27

1472.07

1433.81

1375.71

1327.09

1283.31

1183.56

1092.84

1044.60

1002.47

928.82

766.65

692.43

554.74

Figure S8. IR spectrum of anti-dipyridyldihydrotetraethylcalix[4]pyrrole isomer 2b recorded as

a KBr disc.


S10

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5ppm

gm.tg.492gm/tg/492

Figure S9. 1H NMR (200 MHz) spectrum of the syn isomer 2a in DMSO-d6.


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Figure S10. 1H NMR (200 MHz) spectrum of the anti isomer 2b in DMSO-d6.


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Figure S11. Comparison of the 1H NMR (200 MHz) spectrum of the syn 2a isomer with that of

the anti 2b isomer in DMSO-d6.


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Figure S12. 1H NMR (400 MHz) spectrum of calix[4]phyrin 3 in CDCl3.


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0102030405060708090100110120130140150160170ppm

9.088

28.440

46.500

76.951

77.269

77.587

116.421

123.337

126.127

127.555

135.893

136.884

139.939

149.422

156.312

165.368

Figure S13. 13C{1H} NMR (100.6 MHz) spectrum of calix[4]phyrin 3 in CDCl3.


S15

0102030405060708090100110120130140150160ppm

Figure S14. DEPT-135{1H} NMR (100.6 MHz) spectrum of calix[4]phyrin 3 in CDCl3.


S16

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0

47.9

50

52

54

56

58

60

62

64

66

68

70

72

74

76

78

80

82.7

cm-1

%T

3448.70

2965.35

1577.38

1508.45

1480.14 1460.53

1426.76

1385.881360.65

1317.35

1280.09

1233.87

1201.71

1051.611021.17

992.25

974.56

950.38

888.98

836.28

785.88765.71

718.73

680.64

2929.97

2873.94

Figure S15. IR spectrum of calix[4]phyrin 3 recorded as a KBr disc.


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3. X-ray crystallography

Figure S16. ORTEP diagram of the anti isomers 2b and 2b' generated by the inversion center

with 30% probability ellipsoids.


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4. UV-vis spectrum of calix[4]phyrin

350 400 450 5000.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7 422 nmAb

sorb

ance

wavelength (nm)

Figure S17. UV-vis spectrum of calix[4]phyrin 3 in acetone (ε = 62300 M−1cm−1).


S19

5. NMR titrations and determination of binding constants

Figure S18. 1H NMR (200 MHz) titration spectra of 2a·H2O with the fluoride anion in

DMSO-d6 at room temperature.


S20

Figure S19. Binding constants Ka determination from the slow exchange process

observed during the titration of 2a·H2O with F− as its n-Bu4N+ salt in DMSO-d6 at 298 K.

Figure S20. 1H NMR (200 MHz) titration spectra of 2a·H2O with the chloride anion in


Receptor: F− = 1: 0.206[Ht] = 8.02 × 10−3 M [Gt] = 1.66 × 10−3 M Ka = 25903 M−1

Receptor: F− = 1: 0.412[Ht] = 7.99 × 10−3 M [Gt] = 3.31 × 10−3 M Ka = 70362 M−1


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Figure S21. 1H NMR (200 MHz) titration spectra of 2b·(0.66)H2O with the fluoride anion in



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Figure S22. 1H NMR (200 MHz) titration spectra of 2b·(0.66)H2O with the chloride anion in



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0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.5ppm

0.2 equiv.

0.4 equiv.

0.6 equiv.

0.8 equiv.

1.0 equiv.

1.2 equiv.

1.4 equiv.

1.6 equiv.

1.8 equiv.

2.0 equiv.

2.2 equiv.

2.4 equiv.

2.6 equiv.

2.8 equiv.

3.0 equiv.

3.2 equiv.

Free receptor

Figure S23. 1H NMR titration spectra of 2b·0.66H2O with the dihydrogenphosphate anion in



S24

Figure S24. Determination of Ka using NH resonances by the EQNMR program for the titration of 2a·H2O with Cl− ion in DMSO-d6 at room temperature.

Calculations by WinEQNMR2 Version 2.00 by Michael J. Hynes Program run at 12:11:43 on 10/03/2012 Using NH proton Equilibrium constants are floating point numbers NO. A PARAMETER DELTA ERROR CONDITION DESCRIPTION 1 1 1.04782E+01 1.000E-01 1.482E+00 6.422E+02 K1 2 1 9.41327E+00 9.410E-02 1.831E-03 7.345E+00 free ligand 3 1 1.03400E+01 1.038E-01 9.766E-02 5.603E+02 complex 0RMS ERROR = 2.37E-03 MAX ERROR = 4.40E-03 AT OBS.NO. 16 RESIDUALS SQUARED = 7.32E-05 RFACTOR = 0.0224 PERCENT NO. A EXPT. DEL CALC. DEL RESIDUAL % DEV WEIGHT Cl- Ligand pH 1 1 9.4300E+00 9.4280E+00 1.9732E-03 2.0924E-02 1.0000E+00 1.6600E-03 8.0200E-03 0.0000E+00 2 1 9.4410E+00 9.4423E+00 -1.2922E-03 -1.3687E-02 1.0000E+00 3.3100E-03 7.9900E-03 0.0000E+00 3 1 9.4580E+00 9.4561E+00 1.9121E-03 2.0217E-02 1.0000E+00 4.9500E-03 7.9700E-03 0.0000E+00 4 1 9.4680E+00 9.4696E+00 -1.6136E-03 -1.7043E-02 1.0000E+00 6.5800E-03 7.9400E-03 0.0000E+00 5 1 9.4820E+00 9.4826E+00 -5.8651E-04 -6.1855E-03 1.0000E+00 8.2000E-03 7.9100E-03 0.0000E+00 6 1 9.4930E+00 9.4949E+00 -1.8778E-03 -1.9781E-02 1.0000E+00 9.8100E-03 7.8900E-03 0.0000E+00 7 1 9.5050E+00 9.5069E+00 -1.9293E-03 -2.0298E-02 1.0000E+00 1.1400E-02 7.8600E-03 0.0000E+00 8 1 9.5220E+00 9.5184E+00 3.6011E-03 3.7818E-02 1.0000E+00 1.2990E-02 7.8400E-03 0.0000E+00 9 1 9.5280E+00 9.5298E+00 -1.7538E-03 -1.8407E-02 1.0000E+00 1.4570E-02 7.8100E-03 0.0000E+00 10 1 9.5390E+00 9.5404E+00 -1.4210E-03 -1.4896E-02 1.0000E+00 1.6130E-02 7.7900E-03 0.0000E+00 11 1 9.5610E+00 9.5611E+00 -1.4591E-04 -1.5261E-03 1.0000E+00 1.9240E-02 7.7400E-03 0.0000E+00 12 1 9.5830E+00 9.5808E+00 2.2192E-03 2.3158E-02 1.0000E+00 2.2300E-02 7.6900E-03 0.0000E+00 13 1 9.6010E+00 9.5990E+00 1.9646E-03 2.0462E-02 1.0000E+00 2.5320E-02 7.6400E-03 0.0000E+00 14 1 9.6190E+00 9.6165E+00 2.4700E-03 2.5679E-02 1.0000E+00 2.8310E-02 7.5900E-03 0.0000E+00 15 1 9.6340E+00 9.6328E+00 1.1930E-03 1.2384E-02 1.0000E+00 3.1260E-02 7.5400E-03 0.0000E+00 16 1 9.6440E+00 9.6484E+00 -4.4003E-03 -4.5627E-02 1.0000E+00 3.4170E-02 7.5000E-03 0.0000E+00

TOLERANCE ON SUM OF SQUARES 0.0100 TOLERANCE ON EIGEN VALUES 0.0001 CONVERGANCE AFTER 2 ITERATIONS


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Figure S25. Determination of Ka using NH resonances by the EQNMR program for the titration of 2b·(0.66)H2O with Cl− ion in DMSO-d6 at room temperature.

Calculations by WinEQNMR2 Version 2.00 by Michael J. Hynes Program run at 16:43:16 on 10/04/2012 Using NH proton Equilibrium constants are floating point numbers

NO. A PARAMETER DELTA ERROR CONDITION DESCRIPTION 1 1 9.75334E+00 9.900E-02 1.744E+00 7.591E+02 K1 2 1 9.34261E+00 9.340E-02 2.933E-03 6.851E+00 free ligand 3 1 1.07634E+01 1.075E-01 1.863E-01 6.753E+02 complex 0RMS ERROR = 3.96E-03 MAX ERROR = 5.24E-03 AT OBS.NO. 5 RESIDUALS SQUARED = 2.04E-04 RFACTOR = 0.0375 PERCENT NO. A EXPT. DEL CALC. DEL RESIDUAL % DEV WEIGHT Cl- Ligand pH 1 1 9.3610E+00 9.3637E+00 -2.6779E-03 -2.8607E-02 1.0000E+00 1.6600E-03 8.3800E-03 0.0000E+00 2 1 9.3870E+00 9.3841E+00 2.9192E-03 3.1098E-02 1.0000E+00 3.3100E-03 8.3500E-03 0.0000E+00 3 1 9.4060E+00 9.4038E+00 2.1572E-03 2.2934E-02 1.0000E+00 4.9500E-03 8.3200E-03 0.0000E+00 4 1 9.4270E+00 9.4232E+00 3.8500E-03 4.0840E-02 1.0000E+00 6.5800E-03 8.3000E-03 0.0000E+00 5 1 9.4470E+00 9.4418E+00 5.2433E-03 5.5502E-02 1.0000E+00 8.2000E-03 8.2700E-03 0.0000E+00 6 1 9.4550E+00 9.4595E+00 -4.5490E-03 -4.8112E-02 1.0000E+00 9.8100E-03 8.2400E-03 0.0000E+00 7 1 9.4720E+00 9.4769E+00 -4.8895E-03 -5.1620E-02 1.0000E+00 1.1400E-02 8.2200E-03 0.0000E+00 8 1 9.4930E+00 9.4936E+00 -5.7697E-04 -6.0779E-03 1.0000E+00 1.2990E-02 8.1900E-03 0.0000E+00 9 1 9.5050E+00 9.5100E+00 -4.9868E-03 -5.2465E-02 1.0000E+00 1.4570E-02 8.1600E-03 0.0000E+00 10 1 9.5300E+00 9.5256E+00 4.4413E-03 4.6603E-02 1.0000E+00 1.6130E-02 8.1400E-03 0.0000E+00 11 1 9.5520E+00 9.5560E+00 -4.0035E-03 -4.1913E-02 1.0000E+00 1.9240E-02 8.0800E-03 0.0000E+00 12 1 9.5860E+00 9.5844E+00 1.6298E-03 1.7002E-02 1.0000E+00 2.2300E-02 8.0300E-03 0.0000E+00 13 1 9.6070E+00 9.6112E+00 -4.1542E-03 -4.3241E-02 1.0000E+00 2.5320E-02 7.9800E-03 0.0000E+00 14 1 9.6370E+00 9.6368E+00 2.2984E-04 2.3849E-03 1.0000E+00 2.8310E-02 7.9300E-03 0.0000E+00 15 1 9.6630E+00 9.6608E+00 2.2068E-03 2.2838E-02 1.0000E+00 3.1260E-02 7.8800E-03 0.0000E+00 16 1 9.6870E+00 9.6838E+00 3.2387E-03 3.3433E-02 1.0000E+00 3.4170E-02 7.8300E-03 0.0000E+00

TOLERANCE ON SUM OF SQUARES 0.0100 TOLERANCE ON EIGEN VALUES 0.0001 CONVERGANCE AFTER 2 ITERATIONS


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Figure S26. Determination of Ka using NH resonance by EQNMR for the 2b·0.66H2O and H2PO4

− ion in DMSO-d6 at room temperature.

Calculations by WinEQNMR2 Version 2.00 by Michael J. Hynes Program run at 18:04:09 on 01/15/2013 Using NH proton Equilibrium constants are floating point numbers NO. A PARAMETER DELTA ERROR CONDITION DESCRIPTION 1 1 1.15797E+02 6.000E-01 1.645E+01 9.089E+01 K1 2 1 9.29606E+00 9.360E-02 2.368E-02 5.492E+00 free ligand 3 1 1.12411E+01 1.120E-01 9.364E-02 6.764E+01 complex 0RMS ERROR = 2.28E-02 MAX ERROR = 4.09E-02 AT OBS.NO. 1 RESIDUALS SQUARED = 6.74E-03 RFACTOR = 0.2006 PERCENT NO. A EXPT. DEL CALC. DEL RESIDUAL % DEV WEIGHT H2PO4

- Ligand pH 1 1 9.5170E+00 9.4761E+00 4.0857E-02 4.2931E-01 1.0000E+00 1.6600E-03 8.3800E-03 0.0000E+00 2 1 9.6250E+00 9.6384E+00 -1.3435E-02 -1.3959E-01 1.0000E+00 3.3200E-03 8.3500E-03 0.0000E+00 3 1 9.7600E+00 9.7819E+00 -2.1862E-02 -2.2400E-01 1.0000E+00 4.9600E-03 8.3200E-03 0.0000E+00 4 1 9.8730E+00 9.9084E+00 -3.5351E-02 -3.5806E-01 1.0000E+00 6.5900E-03 8.3000E-03 0.0000E+00 5 1 9.9960E+00 1.0021E+01 -2.5184E-02 -2.5194E-01 1.0000E+00 8.2100E-03 8.2700E-03 0.0000E+00 6 1 1.0134E+01 1.0120E+01 1.4124E-02 1.3937E-01 1.0000E+00 9.8200E-03 8.2400E-03 0.0000E+00 7 1 1.0220E+01 1.0206E+01 1.4003E-02 1.3701E-01 1.0000E+00 1.1420E-02 8.2200E-03 0.0000E+00 8 1 1.0291E+01 1.0282E+01 8.9827E-03 8.7287E-02 1.0000E+00 1.3010E-02 8.1900E-03 0.0000E+00 9 1 1.0364E+01 1.0349E+01 1.4919E-02 1.4395E-01 1.0000E+00 1.4590E-02 8.1600E-03 0.0000E+00 10 1 1.0438E+01 1.0408E+01 3.0091E-02 2.8829E-01 1.0000E+00 1.6150E-02 8.1400E-03 0.0000E+00 11 1 1.0479E+01 1.0461E+01 1.8385E-02 1.7545E-01 1.0000E+00 1.7710E-02 8.1100E-03 0.0000E+00 12 1 1.0515E+01 1.0508E+01 7.4806E-03 7.1142E-02 1.0000E+00 1.9260E-02 8.0800E-03 0.0000E+00 13 1 1.0538E+01 1.0549E+01 -1.1258E-02 -1.0683E-01 1.0000E+00 2.0800E-02 8.0600E-03 0.0000E+00 14 1 1.0570E+01 1.0587E+01 -1.6994E-02 -1.6078E-01 1.0000E+00 2.2330E-02 8.0300E-03 0.0000E+00 15 1 1.0622E+01 1.0621E+01 1.3132E-03 1.2363E-02 1.0000E+00 2.3850E-02 8.0100E-03 0.0000E+00 16 1 1.0641E+01 1.0651E+01 -1.0413E-02 -9.7859E-02 1.0000E+00 2.5360E-02 7.9800E-03 0.0000E+00 TOLERANCE ON SUM OF SQUARES 0.0100 TOLERANCE ON EIGEN VALUES 0.0001 CONVERGANCE AFTER 5 ITERATIONS


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6. H/D Exchange

Figure S27. Partial proton coupled 19F NMR spectrum of the syn isomer with one equiv of F−

ion as its n-Bu4N+ salt in DMSO-d6, showing a broad multiplet for the formation of 1:1 F− ion

complex containing no deuterium atom.


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-87.-86.8-86.5-86.2-85.9-85.6-85.3-85.0-84.7-84.4-84.1-83.8-83.5-83.282.9ppm

Figure S28. Partial proton coupled 19F NMR spectrum of the syn isomer with two equiv of F−

ion as its n-Bu4N+ salt in DMSO-d6, showing a quintet for the formation of 1:1 F− ion complex

containing no deuterium atom.


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Figure S29.The proton coupled 19F NMR spectrum of the syn isomer after the addition of four

equiv of F− ion as its n-Bu4N+ salt in DMSO-d6, showing multiplets for the formation of different

1:1 F− ion complexes containing deuterium atom. The resonances corresponding to the formation

of HF2− (δ = –142.7(d), J(HF) = 117.6 Hz) and DF2

− (δ = –143.2(t), J(DF) = 16.5 Hz) in the

solution are also appeared.


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-86.7-86.5-86.3-86.1-85.9-85.7-85.5-85.3-85.1-84.9-84.7-84.5-84.3-84.183.9ppm

Figure S30. Partial proton coupled 19F NMR spectrum of the syn isomer after the addition of

four equiv of F− ion as its n-Bu4N+ salt in DMSO-d6, showing multiplets for the formation of

different 1:1 F− ion complexes containing deuterium atom.


S31

Figure S31. Partial 1H NMR spectrum recorded after one day for the syn isomer with four equiv

of F− ion as its n-Bu4N+ salt in DMSO-d6, showing appearance of HF2

− with J(HF) = 121 Hz and

the pyrrolic NH resonance split into a doublet. The appearance of the NH resonance even after

the addition of four equiv of F− and 24 h indicates that H/D exchange process can be slow.


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-84.97

-84.45

-84.40

-84.36

-84.31

-83.94

-83.88

-83.85

-83.83

-83.80

-83.76

-83.74

-83.71

-83.65

-83.37

-83.32

-83.29

-83.23

-83.20

-83.14

-83.11

-83.05

-82.81

-82.72

-82.64

-82.55

-82.46

Figure S32. Partial proton coupled 19F NMR spectrum of the anti isomer after the addition of

two equiv of F− ion as its n-Bu4N+ salt in DMSO-d6, showing multiplets for the formation of

different 1:1 F− ion complexes containing deuterium atom.


S33

Figure S33.The proton coupled 19F NMR spectrum of the anti isomer after the addition of three

equiv of F− ion as its n-Bu4N+ salt in DMSO-d6, showing multiplets for the formation of different

1:1 F− ion complexes containing deuterium atom. The resonances corresponding to the formation

of HF2− (δ = –142.6(d), J(HF) = 122.4 Hz) and DF2

− (δ = –143.1(t), J(DF) = 18.8 Hz) in the

solution are also appeared.


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-87.1-86.9-86.7-86.5-86.3-86.1-85.9-85.7-85.5-85.3-85.1-84.9-84.7-84.5-84.3-84.1-83.9-83.7ppm

debasish da/60SKM-SCS-TGSynisomer4eq in DMSO-d6F19 (1H decoupled)

Figure S34.The proton decoupled 19F NMR spectrum of the syn isomer with five equiv of the F−

ion in DMSO-d6, showing one singlet for each type of F− ion complex formed in solution.


S35

Figure S35.The proton decoupled 19F NMR spectrum of the anti isomer with three equiv of the

F− ion in DMSO-d6, showing one singlet for each type of F− ion complex formed in solution as

explained in Fig. 8 of the paper.


S36

Figure S36. Partial 1H NMR spectrum recorded after one day for the anti isomer with three

equiv of F− ion as its n-Bu4N+ salt in DMSO-d6. The NH resonance is completely disappeared

owing to H/D exchange.


The Syn and Anti isomers of the Porphyrinogen-like Precursor of … · 2013. 3. 12. · S5 4000.0...

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