SUPPLEMENTARY INFORMATION
A study of interfacial adsorption isotherm at divided interface for
novel macrocycles in solvent extraction
Halil Zeki Gök a ,, Hasan Demir b
a
b

Department of Chemistry, Osmaniye Korkut Ata University, 80000 Osmaniye, Turkey
Department of Chemical Engineering, Osmaniye Korkut Ata University, 80000 Osmaniye, Turkey
Corresponding author. Tel.: + 90 (328)-827 1000x2539; fax: +90 (328)-825 0097; e-mail:
zekigok@osmaniye.edu.tr, Department of Chemistry, Faculty of Arts and Sciences, Osmaniye Korkut Ata
University, 80000, Osmaniye, Turkey
1. Experimental
1.1. Materials and Equipment
N,N'-(2,2'-(4,5-dicyano-1,2-phenylene)bis(sulfanediyl)bis(2,1-phenylene))bis(2chloroacet-amide) 1 was prepared according to the literature report [1]. Macrocycles 3 and 5
were prepared according to the literature reports [1, 2]. All reagents and solvents were reagent
grade quality and were obtained from commercial suppliers. For synthesis, all solvents were
dried and purified as described by Perrin and Armarego [3]. Demineralized water was used in
extraction experiments. FTIR spectra were measured on a Perkin Elmer Spectrum 65
spectrometer in KBr pellets. 1H and 13C NMR spectra were recorded on a Varian Mercury 400
MHz spectrometer in CDCl3 and DMSO-d6 (99.9%). Mass spectra were measured on a
Micromass Quatro LC/ULTIMA LC-MS/MS spectrometer. Optical spectra were recorded in
the UV-Vis region with a PG-T80+ spectrophotometer in 1 cm path length cuvettes at room
temperature. The elemental analyses were obtained with a LECO Elemental Analyzer (CHNS
0932) spectrophotometer. The melting points were determined with an electrothermal
apparatus and are reported without correction. In solvent extraction experiment Selecta type
shaker with thermostat was used.
116,3
110
562,18
105
100
3051,91
477,79
498,91
950,50
710,13
526,46
95
2923,06
90
1058,79
1159,16
1032,03
1133,82
1107,49
3285,62
85
873,11
917,96
659,40
1226,68
1264,34
2234,99
80
1383,96
1345,48
75
1197,06
1460,71
%T
70
65
60
1295,80
55
764,67
1577,46
1433,59
50
45
40
1682,34
35
1513,38
30,7
4000,0
3600
3200
2800
2400
2000
1800
1600
1400
1200
1000
800
600
450,0
cm-1
Figure S1. The FT-IR spectrum of macrocyclic ligand 2
129,1
125
120
569,91 475,75
497,88
115
529,97
110
2989,23
105
2349,33
3067,67
2956,24
2919,18
3251,78
2860,28
100
1737,82
951,68
1161,41
1199,00
1346,48
1374,22 1266,91
1455,63
1235,04
1220,97
95
2227,54
90
85
1055,11
1033,87
712,35
667,32
872,96
917,91
1103,05
%T
80
1295,22
1435,06
75
763,13
1577,55
70
65
1691,02
60
1517,70
55
50
45
40
37,2
4000,0
3600
3200
2800
2400
2000
1800
1600
cm-1
Figure S2. The FT-IR spectrum of macrocyclic ligand 3
1400
1200
1000
800
600
450,0
89,5
88
86
84
921,95
888,32
82
528,00
1034,83
80
78
1108,65
76
1383,29
1345,99
3275,93
2230,55
74
1221,30
72
2856,12
70
68
%T
1456,53
66
1297,35
64
62
2926,48
60
757,93
1578,55
58
1435,06
56
1688,81
54
52
50
1513,84
48
45,7
4000,0
3600
3200
2800
2400
2000
1800
1600
1400
1200
1000
800
600
450,0
cm-1
Figure S3. The FT-IR spectrum of macrocyclic ligand 4
Date: 20 Aralýk 2011 Salý
88,0
85
80
950,00
1060,12
1032,55
1161,13
1105,78
2915,67
75
479,09
502,88
879,41
918,96
673,10
527,48
1261,38
70
1380,36
3253,86
1223,31
65
2232,25
1347,85
758,36
%T
60
1454,72
55
1299,34
1568,11
50
1435,21
45
1578,94
40
1680,12
1515,01
35
33,0
4000,0
3000
2000
1500
cm-1
Figure S4. The FT-IR spectrum of macrocyclic ligand 5
1000
450,0
Date: 20 Aralýk 2011 Salý
89,5
88
86
84
542,71
480,06
470,36
500,82
615,90
693,24
82
80
78
525,97
3079,56
2920,84
76
918,48
1035,46
74
889,24
3316,78
72
1158,78
2228,75
70
1261,75
1104,12
1384,80
%T
68
1347,01
1213,52
66
64
1452,62
62
1290,59
60
1576,87
1565,11
58
756,57
56
1434,16
54
1688,58
52
1514,53
50
48,8
4000,0
3000
2000
1500
1000
cm-1
Figure S5. The FT-IR spectrum of macrocyclic ligand 6
7.041
7.313
7.536
7.313
7.536
7.553
7.555
7.651
7.550
2.824
2.830
3.508
7.041
7.313
7.536
7.553
7.555
7.651
8.567
8.588
7.600
7.553
7.555
7.651
8.567
8.588
9.819
7.650
7.500
7.450
7.400
7.350
7.300
9.00
8.50
8.00
7.50
0.94
1.82
1.07
1.27
1.06
ppm (t1)
7.00
10.0
ppm (t1)
4.53
2.18
0.85
1.66
1.14
0.98
1.00
1.00
ppm (t1)
5.0
Figure S6. The 1H-NMR spectrum of macrocyclic ligand 2 in CDCl3.
450,0
2.09
2.12
2.13
0.85
1.48
1.05
1.02
0.96
1.00
2.808
3.526
3.803
6.870
7.330
7.618
7.693
8.724
8.745
9.680
5.0
ppm (t1)
Figure S7. The 1H-NMR spectrum of macrocyclic ligand 3 in CDCl3.
1.509
1.672
2.674
3.478
7.081
7.288
7.498
7.633
8.613
8.634
9.963
10.0
ppm (t1)
5.0
Figure S8. The 1H-NMR spectrum of macrocyclic ligand 4 in CDCl3.
3.31
1.47
2.28
2.05
1.62
0.82
1.52
1.04
1.09
1.00
1.700 1.650 1.600 1.550 1.500
ppm (t1)
1.795
2.096
2.523
2.545
2.563
2.581
3.350
3.374
7.029
7.394
7.397
7.413
7.416
7.432
7.435
7.573
7.576
7.593
7.596
7.626
7.630
7.646
7.664
7.668
7.721
7.739
10.049
3.350
3.374
1.795
1.900
1.875
1.850
1.825
1.800
1.775
1.750
1.725
1.700
ppm (t1)
3.500
3.450
3.400
3.350
3.300
3.250
3.200
ppm (t1)
10.00 9.50
ppm (t1)
9.00
8.50
8.00
7.50
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
2.50
2.00
1.50
1.00
Figure S9. The 1H-NMR spectrum of macrocyclic ligand 5 in DMSO-d6.
2.20
2.52
0.91
1.25
2.38
1.07
1.00
-0.003
1.252
1.582
2.835
3.446
6.879
7.260
7.329
7.587
7.606
7.652
8.430
8.451
9.574
5.0
ppm (t1)
Figure S10. The 1H-NMR spectrum of macrocyclic ligand 6 in CDCl3
0.0
32.422
34.579
38.127
76.747
77.065
77.384
113.141
114.828
117.757
122.072
126.404
130.841
132.757
136.283
0
50
100
150
33.101
38.152
71.195
76.743
77.060
77.379
112.795
114.893
115.313
121.583
126.069
128.996
133.398
137.145
140.604
142.160
167.223
ppm (t1)
Figure S12. The 13C-NMR(APT) spectrum of macrocyclic ligand 3 in CDCl3
0
50
100
150
140.077
142.985
166.841
ppm (t1)
Figure S11. The 13C-NMR(APT) spectrum of macrocyclic ligand 2 in CDCl3
26.758
28.203
34.261
38.620
76.735
77.371
113.210
114.735
117.877
121.687
126.197
131.284
0
50
100
150
29.205
33.204
38.162
77.056
112.881
114.858
116.921
122.411
126.539
129.497
133.059
136.656
140.256
142.204
166.557
ppm (t1)
Figure S14. The 13C-NMR(APT) spectrum of macrocyclic ligand 5 in CDCl3
0
50
100
150
132.650
135.972
140.102
143.273
167.046
ppm (t1)
Figure S13. The 13C-NMR(APT) spectrum of macrocyclic ligand 4 in CDCl3
33.541
38.117
77.027
112.798
114.895
116.337
122.834
126.620
128.650
Figure S15. The 13C-NMR(APT) spectrum of macrocyclic ligand 6 in CDCl3
0
50
100
150
133.241
137.102
140.017
141.714
166.145
ppm (t1)
References
[1]
H.Z. Gök, B. Farsak, Synthesis, characterisation and aggregation properties of novel
metal-free and metallophthalocyanines containing four 21-membered oxatetrathiadiaza
macrocycles, J. Organomet. Chem. 735 (2013) 65-71.
[2]
H.Z. Gök, B. Farsak, Synthesis and spectral properties of novel metal-free and
metallophthalocyanines bearing four 19-membered tetrathiadiaza macrocycles, J. Mol.
Struct. 1054-1055 (2013) 25-31.
[3]
D.D. Perrin, W.L.F. Armarego, Purification of Laboratory Chemicals. 2nd ed.,
Pergamon Press, Oxford, 1989.
Appendix A. Supplementary material Additional data associated with this article are given in
Online Resource 1