Synthesis and characterization of novel phthalocyanines with four tridentate NNS substituents and four chloro groups

Abstract

Two new 4,5-disubstituted phthalonitrile derivatives have been prepared from tridentate amine thiol reactants obtained by reducing directly two different benzothiazolines. Novel metal free phthalocyanines and divalent metal phthalocyanines carrying four tridentate NNS substituents in addition to four chloro groups on peripheral positions have been synthesized from the corresponding phthalonitrile derivatives in the presence of a suitable anhydrous metal salt [Zn(CH₃CO₂)₂ or NiCl₂] or 2-(dimethylamino)ethanol. A lutetium(III) bis(phthalocyaninate) complex that is highly soluble in most organic solvents has been synthesized from reaction of one of the phthalonitrile derivatives with anhydrous lutetium(III) acetate in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu) in 1-hexanol. The newly synthesized compounds have been characterized by elemental analyses, IR, ¹H, ¹³C NMR, MS, UV/VIS, ESR, and atomic absorption spectroscopy. Cyclic voltammetric measurements of the novel compounds have been made.

References

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. Bekaroǧlu 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.
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.
10. T. Komatsu, K. Ohta, T. Fujimoto and I. Yamamoto, J. Mater. Chem., 1994, 4, 533.
11. A. Pandoven, Y. Cozien and M. L'Her, New. J. Chem., 1991, 15, 515.
12. A. Pandoven, Y. Cozien and M. L'Her, New. J. Chem., 1992, 16, 711.
13. M. Hanack, S. Deger and A. Lange, Coord. Chem. Rev., 1988, 83, 115.
14. S. A. Mikhalenko, S. V. Barkanova, O. L. Lebedev and E. A. Luk'yanets, Zh. Obshch. Khim., 1971, 41, 2735.
15. A. R. Koray, V. Ahsen and Ö. Bekaroǧlu, J. Chem. Soc., Chem. Commun., 1986, 932; V. Ahsen, E. Yílmazer, M. Ertaş and Ö. Bekaroǧlu, J. Chem. Soc., Dalton Trans., 1988, 401; V. Ahsen, A. Gürek, E. Musluoǧlu, A. Gül and Ö. Bekaroǧlu, Helv. Chim. Acta, 1990, 73, 174.
16. M. Koçak, A. Cihan, A. I. Okur and Ö. Bekaroǧlu, J. Chem. Soc., Chem. Commun., 1991, 578; A. Gürek, V. Ahsen, A. Gül and Ö. Bekaroǧlu, J. Chem. Soc., Dalton Trans., 1991, 3367.
17. G. Gümüş, Z. Öztürk, V. Ahsen, A. Gül and Ö. Bekaroǧlu, J. Chem. Soc., Dalton Trans., 1992, 2485.
18. I. Yílmaz and Ö. Bekaroǧlu, Chem. Ber., 1996, 129, 967.
19. M. Koçak, A. I. Okur and Ö. Bekaroǧlu, J. Chem. Soc., Dalton Trans., 1994, 323.
20. A. Gürek and Ö. Bekaroǧlu, Helv. Chim Acta, 1994, 77, 1616.
21. A. G. Gürek and Ö. Bekaroǧlu, J. Porph. Phthalocyan., 1997, 1, 227.
22. Z. Altuntaş Bayír, E. Hamuryudan, A. G. Gürek and Ö. Bekaroǧlu, J. Porph. Phthalocyan., 1997, 1, 349.
23. M. Kandaz and Ö. Bekaroǧlu, Chem. Ber., 1997, 130, 833.
24. E. Musluoǧlu, V. Ahsen, A. Gül and Ö. Bekaroǧlu, Chem. Ber., 1991, 124, 2531.
25. Z. Z. Öztürk, E. Musluoǧlu, V. Ahsen, A. Gül and Ö. Bekaroǧlu, J. Mater. Sci., 1992, 27, 6183.
26. S. A. Mikhalenko, V. M. Derkacheva and E. A. Luk'yanets, Zh. Obshch. Khim., 1981, 51, 1650.
27. M. J. Cook, A. J. Dunn, S. D. Howe, A. J. Thomson and K. J. Harrison, J. Chem. Soc., Perkin Trans. 1, 1988, 2453.
28. W. Eberhardt and M. Hanack, Synthesis, 1997, 95.
29. N. B. McKeown, Phthalocyanine Materials, Synthesis, Structure and Function, Cambridge University Press, 1998.
30. H. Matsuda, S. Okada, A. Masaki, H. Nakanishi, Y. Suda, K. Shigehara and A. Yamada, Proc. SPYE-Int. Soc. Opt. Eng., 1990, 105, 1337.
31. D. Wöhrle, M. Eskes, K. Shigehara and A. Yamada, Synthesis, 1993, 194.
32. S. Hayashida and N. Hayashi, Chem. Lett., 1990, 2137.
33. M. N. Golovin, P. Seymour, K. Jayaraj, Y. Fu and A. B. P. Lever, Inorg. Chem., 1990, 29, 1719.
34. M. L. Rodriguez-Mendez and R. Aroca, Chem. Mater., 1993, 5, 933.
35. I. Gürol, V. Ahsen and Ö. Bekaroǧlu, J. Chem. Soc., Dalton Trans., 1994, 497.
36. A. Gürek and Ö. Bekaroǧlu, J. Chem. Soc., Dalton Trans., 1994, 1419.
37. M. Hanack, G. Schmid and M. Sommerauer, Angew. Chem., Int. Ed. Engl., 1993, 32, 1422; Angew. Chem., 1993, 105, 1540.
38. G. Schmid, M. Sommerauer, M. Geyer and M. Hanack, in Phthalocyanines: Properties and Application, eds. C. C. Leznoff and A. B. P. Lever, VCH, New York, 1996, vol. 4, p. 83.
39. M. Hanack and M. Lang, Chemtracts-Org. Chem., 1995, 8, 131; Adv. Mater., 1994, 6, 822.
40. M. Sommerauer, C. Rager and M. Hanack, J. Am. Chem. Soc., 1996, 118, 10085.
41. C. C. Leznoff, S. M. Marcuccio, S. Greenberg, A. B. P. Lever and K. B. Tomer, Can. J. Chem., 1985, 63, 623.
42. C. C. Leznoff, M. Hu, C. R. McArthur, Y. Qín and J. E. Van Lier, Can. J. Chem., 1994, 72, 1990.
43. P. Haisch and M. Hanack, Synthesis, 1995, 1251.
44. D. Masural, C. Sirlin and J. Simon, New. J. Chem., 1987, 11, 455.
45. K. Takahashi, M. Kawashima, Y. Tomito and M. Itoh, Inorg. Chim Acta, 1995, 232, 69.
46. M. Hossain and S. Ghosh, Transition Met. Chem., 1997, 497, 22.
47. U. Brand and H. Vahrenkamp, Chem. Ber., 1996, 129, 431.
48. A. G. Gürek and Ö. Bekaroǧlu, J. Porph. Phthalocyan., 1997, 1, 67.
49. J. F. van der Pol, E. Neeleman, J. C. van Miltenburg, J. W. Zwikker, R. J. M. Nolte and W. Drenth, Macromolecules, 1990, 23, 155.
50. S. Gaspard and P. Maillard, Tetrahedron, 1987, 43, 1083.
51. G. Gümüş, A. Gül and Ö. Bekaroǧlu, J. Chem. Res. (S), 1994, 430.
52. D. Wohrle and V. Schmidt, J. Chem. Soc., Dalton Trans., 1988, 549.
53. D. Wohrle and B. Schulte, Makromol. Chem., 1988, 189, 1167.
54. H. Tomoda, S. Saito, S. Ogawa and S. Shiraishi, Chem. Lett., 1980, 1277.
55. T. Toupance, P. Bassoul, L. Mineau and J. Simon, J. Phys. Chem., 1996, 100, 11704.
56. C. Clarisse and M. T. Riou, Inorg. Chim. Acta, 1987, 130, 139.
57. H. F. Shurvell and L. Pinzutti, Can. J. Chem., 1966, 44, 125.
58. T. Toupance, V. Ahsen and J. Simon, J. Am. Chem. Soc., 1994, 116, 5352.
59. H. Konami, M. Hatano and A. Tajiri, Chem. Phys. Lett., 1989, 160, 163.
60. M. L. Rodriguez-Mendez and R. Aroca, Chem. Mater., 1992, 4, 1017.
61. D. Battisti, L. Tomilova and R. Aroca, Chem. Mater., 1992, 4, 1323.
62. F. Guyon, A. Pandoven, P. Guenot and M. L'Her, Inorg. Chem., 1994, 33, 4787.
63. M. Bouvet and J. Simon, Chem. Phys. Lett., 1990, 172, 299.
64. F. Guyon, A. Pandoven, J. Kerbaol and M. L'Her, Inorg. Chem., 1998, 37, 569.
65. A. De Cian, M. Moussavi, J. Fischer and R. Weiss, Inorg. Chem., 1985, 24, 3162.
66. C. Piechocki and J. Simon, J. Chem. Phys. Lett., 1985, 122, 124.
67. G. A. Corker, B. Grant and N. J. Clecak, J. Electrochem. Soc., 1979, 126, 1339.
68. T. Nyokong, Polyhedron, 1993, 12, 375.
69. R. H. Campbell, G. A. Heath, G. T. Hefter and R. C. S. McQueen, J. Chem. Soc., Chem. Commun., 1983, 1123.
70. A. Giraudeau, A. Louati, M. Gross, J. J. Andre, J. Simon, C. H. Su and K. M. Kadish, J. Am. Chem. Soc., 1983, 105, 2917.
71. J. T. S. Irvine and B. R. Eggins, J. Electroanal. Chem., Interfacial Electrochem., 1989, 271, 161.
72. A. R. Özkaya, A. I. Okur, A. Gül and Ö. Bekaroǧlu, J. Coord. Chem., 1994, 33, 311.
73. L. D. Rolmann and R. T. Iwamoto, J. Am. Chem. Soc., 1968, 90, 1455.
74. A. Giraudeau, F. F. Fan and A. J. Bard, J. Am. Chem. Soc., 1980, 102, 5137.
75. A. R. Özkaya, A. G. Gürek, A. Gül and Ö. Bekaroǧlu, Polyhedron, 1997, 16, 1877.
76. A. R. Özkaya, I. Yílmaz and Ö. Bekaroǧlu, J. Porph. Phthalocyan., 1998, 2, 483.
77. A. Rosa and A. J. Baerends, Inorg. Chem., 1994, 33, 584.
78. D. W. Clack, N. S. Hush and I. S. Woolsey, Inorg. Chim. Acta, 1976, 19, 129.
79. D. Lexa and M. Reix, J. Chim. Phys., 1974, 71, 511.
80. E. Ough, T. Nyokong, K. A. M. Creber and M. J. Stillmann, Inorg. Chem., 1988, 27, 2724.
81. D. D. Perrin and W. L. F. Armarego, Purification of Laboratory Chemicals, 2nd edn., Pergamon, Oxford, 1980.