SUPPLEMENTARY INFORMATION

The effects of substituent position on kinetics of benzene vapour adsorption onto 3-

phenylphenoxy substituted metal-free and metallo-phthalocyanines thin films

Haytham Elzien Alamin Alia,b, Nursel Canc, Selçuk Altuna*, Zafer Odabaşa**

aDepartment of Chemistry, Marmara University, Istanbul, 34722, Turkey. bUniversity Of Khartoum, Department of Chemistry, Faculty of Science, P.O. Box 321, Khartoum, 11115, Sudan cDepartment of Physics, Yıldız Technical University, Esenler, Istanbul, 34210, Turkey.

1. Materials and Equipment

All chemicals were used reagent grade quality. 3-nitrophthalonitrile, 4-nitrophthalonitrile, 3-

phenylphenol and metal salts were purchased from Alfa Aesar, Fluka, Merck and used as

received. The solvents were purified, dried and stored over molecular sieves (4Å). All

reactions were carried out under dry nitrogen atmosphere unless otherwise noted. The

preparation of 3-phenylphenoxy substituted phthalonitriles (1 and 2) was achieved by the

reaction of 3-phenylphenol with 3-nitrophthalonitrile or 4-nitrophthalonitrile through base

catalysed nucleophilic aromatic displacement reaction. The novel Pcs (3-10) were

successively cleaned by washing with hot acetic acid-water solution by volume 7/3, water,

ethanol, and acetonitrile in a Soxhlet apparatus. Column chromatography was performed on

silica gel 60 for a proper purification of the raw compounds. The purity of the products was

tested in each step by thin layer chromatography (Silica-gel F-254 coated TLC plate). Melting

points of the Pc compounds were found to be higher than 300ο C. IR Spectra and electronic

spectra were recorded on a Shimadzu FTIR-8300 (ATR) and a Shimadzu UV–1601

spectrophotometer, respectively. Elemental analyses were performed by the Instrumental

Analysis Laboratory of TUBITAK–Ankara. Mass spectra were acquired on a Microflex III

MALDI-TOF mass spectrometer (Bruker Daltonics, Germany) equipped with a nitrogen UV–

Laser operating at 337 nm in reflectron mode with an average of 50 shots.

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2016

1. Spectral Studies

Fig. S1. 1H-NMR spectra of starting material 1 in d-CHCl3 at aromatic region.

dd:7.61(7.72;2.05 Hz)

t:7.607.40 Hz

CN

CN

Odd:7.59

(7.72;2.52 Hz)

dd:7.11(8.83;2.52 Hz)

dd:7.18(8.67;2.05 Hz)

t:7.427.25 Hz

d:7.362.35 Hz

d:7.547.72 Hz

t:7.487.25 Hz

t:7.497.41 Hz

Fig. S2. 1H-NMR spectra of starting material 2 in d6-DMSO at aromatic region.

Fig. S3. MALDI-TOF-MS mass spectrum of alpha-substituted 2HPc 3 in 2,5-dihydroxy-

benzoic acid MALDI matrix accumulating 50 laser shots.

t: 7.39 ppm(7.40 Hz)

CN

CNOt: 7.49 ppm(7.25 Hz)

dd: 7.70ppm(8.35;2.30 Hz)

dd: 7.30ppm(8.83;2.05 Hz)

dd: 7.31 ppm(8.83;2.05Hz)

d: 7.79 ppm(2.10Hz)

d: 7.86 ppm(2.68 Hz)

d: 8.12 ppm(8.67 Hz)

dd: 7.45ppm(8.67;2.68 Hz)

m: 7.80ppm

Fig. S4. MALDI-TOF-MS mass spectrum of beta-substituted 2HPc 4 in 2,5-dihydroxy-

benzoic acid MALDI matrix accumulating 50 laser shots.

Fig. S5. MALDI-TOF-MS mass spectrum of alpha-substituted ZnPc 5 in 2,5-dihydroxy-

benzoic acid MALDI matrix accumulating 50 laser shots.

Fig. S6. MALDI-TOF-MS mass spectrum of beta-substituted ZnPc 6 in 2,5-dihydroxy-

benzoic acid MALDI matrix accumulating 50 laser shots.

Fig. S7. MALDI-TOF-MS mass spectrum of alpha-substituted In(OAc)Pc 7 in 2,5-dihydroxy-

benzoic acid MALDI matrix accumulating 50 laser shots.

Fig. S8. MALDI-TOF-MS mass spectrum of beta-substituted In(OAc)Pc 8 in 2,5-dihydroxy-

benzoic acid MALDI matrix accumulating 50 laser shots.

Fig. S9. MALDI-TOF-MS mass spectrum of alpha-substituted CuPc 9 in 2,5-dihydroxy-

benzoic acid MALDI matrix accumulating 50 laser shots.

Fig. S10. MALDI-TOF-MS mass spectrum of beta-substituted CuPc 10 in 2,5-dihydroxy-

benzoic acid MALDI matrix accumulating 50 laser shots.

Table. S1. IR data of starting materials and phthalocyanines

Pcs (>N-H str.) (=C-H str.) (--CH3 str.) -CN str (C=O str) (C=C str.) (N-H bend) (C-H bend) (Ar-O-Ar str.) (C-N str.) (C-C str.),

1 - 3084.35 - 2228.40 - 1567.08 - 1475.17 1459.39 1268.97 - 1172.39

1051.02

2 - 3064.28 -2230.00

- 1587.71 -1482.05 1453.54 1405.40

1278.00 1242.64 - 1083.91

1008.78

3 3287.91 3057.40 - - - 1637.73 1567.25 1503.43 1453.29

1332.73 1288.65 1246.78

1181.62 1179.15

1088.92 1045.67 1029.08

4 3289.68 3060.56 - - - 1585.23 1568.97 1501.26 1469.98

1417.24

1308.17 1261.01 1218.84

1181.62 1158.90 1090.25

5 - 3043.65 - - - 1568.11 - 1473.96 1417.15

1328.86 1236.20 1120.24 1081.03

6 - 3060.67 - - -1586.441570.50 - 1468.18

1399.87

1341.10 1285.14 1261.49

1219.09 1181.94 1158.60

1089.91 1054.79

7 - 3056.41 2840.74 - 1715.34 1567.74 - 1474.00 1417.88

1329.35 1288.28 1234.68

1181.64 1158.57

1046.83 1006.27

8 - 3060.71 2890.12 - 1720.30 1586.18 1570.59 -

1470.18 1418.46 1396.83

1331.69 1261.28

1219.56 1181.65

1078.87 1044.55

9 - 3026.43 - - - 1605.23 - 1580.64 1477.42

1332.70 1287.56

1219.29 1166.14

1086.87 1003.68 1047.99

10 - 3030.95 - - - 1580.77 1511.77 - 1477.63 1330.70

1287.861220.00 1167.98

1090.56 1003.32

Table. S2. UV-vis data of phthalocyanines in toluene at 1.10-5 mol.dm-3

Pcs B Band Vibr. Band Vibr. Band Q1 Band Q2 Band Red Shift3 331(4.605) 622(4.378) 656(4.491) 687(4.974) 717(5.003) 17 nm4 341(4.832) 607(4.474) 638(4.657) 666(5.010) 700(5.038)5 332(4.322) 627(4.258) 697(5.009) - 14 nm6 339(4.793) 615(4.577) 683(5.088) -7 335(4.430) 639(4.255) 710(5.024) - 10 nm8 356(4.705) 638(4.297) 700(5.033) -9 339(4.438) 623(4.301) 692(5.046) - 12 nm10 356(4.634) 612(4.322) 680(5.086) -