129.48, 133.46, 134.33 (aromatic CH), 135.27 (aromatic C),
137.17–137.84 (aromatic CH), 145.42 (aromatic C), 149.00
(aromatic CH), 149.56 (aromatic C) and 158.74 (pyridine C).
MS (FAB): m/z 377 (100, Mϩ), 298 (3, M Ϫ C5H5N), 249 (1)
and 183 (10%).
1H NMR (d6-dmso): δ 4.48 (s, 8 H, CH2), 5.54 (s, 4 H, NH),
7.10–8.75 (m, 40 H, aryl H). Yield of 2 0.094 g (45%),
mp > 200 ЊC. νmax
/cmϪ1 3395–3390 (NH), 3080, 3008, 2978,
˜
2902, 2876 (alkyl CH), 1600, 1585, 1575 (C᎐N), 1525, 1495,
᎐
1445, 1420, 1395, 1280, 1210, 1140, 960, 790, 757, 705 and 667.
1H NMR (d6-dmso): δ 1.24 (d, 12 H, CH3), 4.21 (t, 4 H, NCH),
5.54 (s, 4 H, NH), 6.82–8.57 (m, 40 H, aryl H). MS (FAB):
m/z 1629 [5, (M ϩ 2)ϩ] and 1311 [12, M Ϫ 4(C5H5N)].
1-Chloro-3,4-dicyano-6-[2-(2-pyridylethylamino)phenyl-
sulfanyl]benzene IV. Compound II (1.00 g, 4.62 mmol) and 1,2-
dichloro-4,5-dicyanobenzene (0.46 g, 2.32 mmol) were dissolved
in tetrahydrofuran (120 cm3) under nitrogen. After stirring for
10 min finely ground anhydrous potassium carbonate (1.15 g,
8.26 mmol) was added with stirring. The reaction mixture was
stirred under nitrogen at reflux temperature for 48 h. After cool-
ing the yellowish green mixture was filtered and the solvent
evaporated to dryness. The resulting oily residue was extracted
with n-hexane (3 × 25 cm3). The combined extracts were kept at
Ϫ30 ЊC for 24 h. The cold mother-liquor was decanted off the
yellow precipitate which was dried in vacuo at room temper-
ature. Compound IV is soluble in chloroform, dichloro-
methane, ethanol, acetone, thf, Et2O, dmf and dmso. Yield 0.36
Nickel(II) phthalocyaninates 3 and 4. A mixture of compound
III (0.200 g, 0.0531 mmol) or IV (0.200 g, 0.512 mmol),
anhydrous NiCl2 (0.0179 g, 0.131 mmol) and quinoline (5 cm3)
was heated and stirred at 175 ЊC for 5 h under nitrogen. After
having cooled to 60 ЊC, it was filtered and the dark green pre-
cipitate refluxed several times with water, ethanol, chloroform
and acetone to remove unchanged materials. The solid was
heated at 60 ЊC with dmf (2 × 10 cm3) and dmso (2 × 10 cm3)
and filtered off. Finally the dark green 3 and 4 were obtained by
washing with ethanol and diethyl ether, then, dried in vacuo
at 100 ЊC. These compounds are slightly soluble in dmf, dmso
/cmϪ1 3395, 3390 (NH), 3074, 3004,
and pyridine. Yield of 3 0.06 g (29%), mp > 200 ЊC. νmax
/cmϪ1
˜
g (20%), mp 124 ЊC. νmax
2956, 2918, 2866 (alkyl CH), 2225 (C᎐N), 1589–1566 (pyridine
˜
᎐
3390 (NH), 3074, 3004, 2975–2866 (alkyl CH), 1600, 1589,
᎐
C᎐N), 1501, 1480, 1445, 1425, 1366, 1292, 1225, 1121, 933, 785,
750, 708, 700 and 667. H NMR (d6-dmso): δ 1.40 (d, 3 H,
1566 (C᎐N), 1530, 1465, 1431, 1390, 1150, 970, 780, 757, 704
᎐
᎐
1
and 665. Yield of 4 0.0399 (19%), mp > 200 ЊC. νmax
˜
/cmϪ1 3395–
CH3), 4.76 (qnt, 1 H, NCH), 5.88 (d, 1 H, NH), 6.69–7.72 (m,
9 H, aryl H) and 8.41 (pyridine Ha). 13C NMR (APT) (d6-
dmso): δ 22.43 (CH3), 53.35 (NCH), 108.60 (aromatic C),
112.78 (aromatic CH), 113.72 (aromatic C), 115.12–115.50
3390 (NH) 2978–2865 (alkyl CH), 1600, 1588, 1567 (C᎐N),
1535, 1470, 1420, 1380, 1150, 975, 790, 757, 700 and 665.
᎐
Lutetium(III) bis(phthalocyaninate) 5. A mixture of com-
pound III (0.200 g, 0.531 mmol), anhydrous lutetium()
acetate (0.032 g, 0.264 mmol) and dbu (0.317 g, 2.112 mmol) in
1-hexanol (1.5 cm3) was heated at reflux under nitrogen for 20 h.
After cooling to room temperature, it was treated with ethanol
(5 cm3) and the dark green precipitate filtered off and then
washed with hot ethanol several times. The crude product was
extracted with chloroform (5 × 20 cm3). The remaining green
solid was identified by visible spectroscopy as being the free
phthalocyanine. The green solution was reduced in volume on a
rotary evaporator and then chromatographed on a column of
silica gel using CH3OH–CH2Cl2 (1:20, v/v) as eluent. The green
product is soluble in chloroform, dichloromethane, acetone,
thf, dmf and dmso. Yield of 5 0.085 g (40%), mp > 200 ЊC.
᎐
(C᎐N), 118.82–120.75, 122.53, 129.65, 133.47, 134.39 (aromatic
᎐
CH), 135.70 (aromatic C), 137.28–137.88 (aromatic CH),
146.10 (aromatic C), 149.04 (aromatic CH), 149.40 (aromatic
C) and 162.73 (pyridine C). MS (FAB): m/z 391 (100, Mϩ), 312
(7, M Ϫ C5H5N) and 106 (25%).
Metal-free phthalocyanines V and VI. A solution of complex
III (0.188 g, 0.50 mmol) or IV (0.200 g, 0.50 mmol) in dry
2-(dimethylamino)ethanol (1 cm3) was refluxed under nitrogen
for 2 h. After cooling, ethanol (10 cm3) was added in order to
precipitate the product. The green product was filtered off
and refluxed several times with ethanol to remove unreacted
organic materials. The crude products were purified by column
chromatography (silica gel, CH2Cl2–n-hexane 5:2). The pro-
ducts were soluble in dmf and dmso. Yield of V 0.039 g (21%),
νmax
/cmϪ1 3390 (NH), 3055, 3009, 2953–2827 (alkyl CH), 1600,
˜
1588, 1574 (C᎐N), 1523, 1497, 1485, 1472, 1446, 1421, 1395,
᎐
mp > 200 ЊC. νmax
/cmϪ1 3390 (NH), 3285 (NH), 3079, 3009,
˜
1290, 1220, 1140, 961, 820, 790, 757, 706 and 667. 1H NMR (d6-
dmso): δ 4.44 (s, 16 H, CH2), 5.95 (s, 8 H, NH) and 6.97–8.25
(m, 64 H, aryl H).
2983–2890 (alkyl CH), 1600, 1588, 1566 (C᎐N), 1501, 1482,
᎐
1446, 1425, 1368, 1290, 1225, 1120, 934, 790, 757, 708, 700 and
1
667. H NMR (d6-dmso): δ Ϫ4.29 (s, 2 H, NH), 4.40 (s, 8 H,
CH2), 5.40 (s, 4 H, NH), 6.47–8.26 (m, 40 H, aryl H). Yield of
/cmϪ1: 3395–3390 (NH),
Acknowledgements
VI 0.040 g (20%), mp > 200 ЊC. νmax
˜
3285 (NH), 3049, 3004, 2954, 2908, 2858 (alkyl CH), 1600,
The authors thank A. R. Özkaya for cyclic voltammetry meas-
urements. Ö. B. is grateful to the Turkish Academy of Science
(TUBA) and the Research Fund of the Technical University of
Istanbul for their support.
1587, 1566 (C᎐N), 1502, 1462, 1424, 1412, 1366, 1293, 1224,
᎐
1
1120, 933, 786, 757, 708, 700 and 665. H NMR (d6-dmso):
δ Ϫ4.29 (s, 2 H, NH), 1.36 (s, 12 H, CH3), 4.78 (s, 4 H, NCH),
5.40 (s, 4 H NH), 6.42–8.23 (m, 40 H, aryl H). MS (FAB):
m/z 1564 (8, Mϩ) and 1248 [18%, M Ϫ 4(C5H5N)].
References
Zinc(II) phthalocyaninates 1 and 2. A mixture of compound
III (0.193 g, 0.514 mmol) or IV (0.200 g, 0.512 mmol),
anhydrous zinc acetate (0.023 g, 0.128 mmol) and quinoline (0.5
cm3) was heated and stirred at 175 ЊC in a sealed glass tube for 5
h under nitrogen. After cooling to room temperature, ethanol
(5 cm3) was added in order to precipitate the product. The dark
green product was filtered off and then washed several times
successively with hot water, hot EtOH, hot chloroform and
diethyl ether. It was isolated by silica gel column chromato-
graphy with chloroform–methanol (20:1 v/v) as eluent. These
products are soluble in dmf, dmso and pyridine. Yield of 1
1 C. C. Leznoff and A. B. P. Lever (editors), Phthalocyanines
Properties and Applications, VCH, New York, 1989–1996, vols. 1–4.
2 P. Gregory, High Technology Applications of Organic Colorants,
Plenum, New York, 1991.
3 I. Rosenthal, Photochem. Photobiol., 1991, 53, 859.
4 Z. Z. Öztürk, R. Zhou, U. Weimar, V. Ahsen, Ö. Bekarogˇlu and
W. Göpel, Sens. Actuators, B, 1995, 26–27, 208.
5 M. Maitrot, G. Guillaud, B. Boudjema, J. J. Andre, H. Strzelecka,
J. Simon and R. Even, Chem. Phys. Lett., 1987, 133, 59.
6 Y. Liu, K. Shigehara, M. Hara and A. Yamada, J. Am. Chem. Soc.,
1991, 113, 440.
7 J. S. Shirk, J. R. Lindle, F. J. Bartoli and M. E. Boyle, J. Phys. Chem.,
1992, 96, 5847.
0.104 g (52%), mp > 200 ЊC. νmax
/cmϪ1 3390 (NH), 3080, 3009,
˜
8 M. M. Nicholson, Ind. Eng. Chem. Prod. Res. Dev., 1982, 21, 261.
9 C. Piechocki, J. Simon, J. J. Andre, D. Guillon, P. Petit, A. Skoulios
and P. Weber, Chem. Phys. Lett., 1985, 122, 124.
2978–2876 (alkyl CH), 1600, 1588, 1570 (C᎐N), 1522, 1497,
᎐
1446, 1421, 1395, 1290, 1220, 1140, 961, 790, 757, 706 and 667.
J. Chem. Soc., Dalton Trans., 1999, 4503–4510
4509