Thiadiazole-derived expanded heteroazaporphyrinoids

Organic Letters

Volumn 3, Issue 14, 2001, Pages 2153-2156

  Islyaikin, Mikhail K ^a,b   Danilova, Elena A ^b   Yagodarova, Larisa D ^b   Rodríguez Morgade, M Salomé ^a   Torres, Tomás ^a  

^a UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

^b IVANOVO STATE UNIVERSITY OF CHEMISTRY AND TECHNOLOGY   (Russian Federation)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000784405     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol015924l     Document Type: Article

References (46)

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2. (b) The Porphyrin Handbook; Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press: Sun Diego, CA, 1999; Vol. 2.
3. See for example: (a) Sridevi, B., Seenichamy, J. N.; Rao, R.; Chandrashekar, T. K. Inorg. Chem. 2000, 39, 3669.
4. (b) Sessler, J. L. Weghorn, S. J. Expanded, Contracted and Isomeric Porphyrins; Elsevier: Oxford, 1997.
5. (c) Allen, W. A.; Sessler, J. L. Chem. Technol. 1999, 29, 16.
6. See for example: (a) Sessler, J. L.; Murai, T.; Hemmi, G. Inorg. Chem. 1989, 28, 3390.
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9. (d) Johnson, M. R.; Miller, D. C.; Bush, K.; Becker, J. J.; Ibers, J. A. J. Org. Chem. 1992, 57, 11763.
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11. (a) Sessler, J. L.; Mody, T. D.; Lynch, V. Inorg. Chem. 1992, 31, 529.
12. (b) Marks, T. J.; Stojakovic, D. R. J. Am. Chem. Soc. 1978, 100, 1695.
13. (c) Day, V. W.; Marks, T. J.; Wachter, W. A. J. Am. Chem. Soc. 1975, 97, 4519.
14. For general overviews in this field see: (a) Phthalocyanines, Properties and Applications; Leznoff, C. C., Lever, A. B. P., Eds.; VCH Publishers: Weinheim, 1989, 1993, 1996; Vols. 1-4.
15. (b) Hanack, M.; Heckmann, H.; Polley, R. In Methods of Organic Chemistry (Houben-Weyl); Schaumann, E., Ed.; Georg Thieme Verlag: Stuttgart, 1998; Vol. E 9d, p 717. For selected papers of our group see:
16. (c) de la Torre, G.; Martínez-Díaz, M. V.; Ashton, P. R.; Torres, T.; J. Org. Chem. 1998, 63, 8888.
17. (d) Maya, E. M.; Vázquez, P.; Torres, T.; Gobi, L.; Diederich, F.; Pyo, S.; Echegoyen, L. J. Org. Chem. 2000, 65, 823.
18. Fernández-Lázaro, F.; Torres, T.; Hauschel, B.; Hanack, M. Chem. Rev. 1998, 98, 563.
19. (a) de la Torre, G.; Nicolau, M.; Torres, T. Phthalocyanines: Synthesis, Supramolecular Organization and Physical Properties. In Supramolecular Photosensitive and Electroactive Materials; Nalwa, H. R., Ed.; Academic Press: New York, 2001; pp 1-111.
20. (b) Gouloumis, A.; Liu, S-. G.; Sastre, A.; Vázquez, P. Echegoyen, L.; Torres, T. Chem. Eur. J. 2000, 6, 3600.
21. (a) del Rey, B.; Keller, U.; Torres, T.; Rojo, G.; Agulló-López, F.; Nonell, S.; Martí, C.; Brasselet, S.; Ledoux, I.; Zyss, J. J. Am. Chem. Soc. 1998, 120, 12808.
22. (b) Claessens, C. G.; Torres, T. Chem. Eur. J. 2000, 6, 2168.
23. Rodríguez-Morgade, M. S.; Cabezón, B.; Esperanza, S.; Torres, T. Chem. Eur. J. In press.
24. max 278 (4.71), 392 (4.88), 413 (4.89), 463 (4.25), 501 nm (4.10).
25. Metal complexes [Zn(II) and Al(III)] of unsubstituted compound 2 have been described previously by one of us: Kudrik, E. V.; Islyaikin, M. K.; Smirnov, R. P. Zh. Org. Chim. 1997, 33, 1107. However, this is the first time that a free-base of this class of compounds, which we named thiadiazolephthalocyanines, is reported. Their electronic features are in good agreement with the 18 π-electron aromatic structure proposed for this system. The UV/vis spectrum of 2 (Figure 1) shows a group of bands in the visible range at 530, 564, and 615 nm, bathochromically shifted when compared with nonaromatic hemiporphyrazines. Therefore, compound 2 is electronically similar to the metalated complexes mentioned above and resembles its close relatives the triazolephthalocyanines: (a) Nicolau, M.; Cabezón, B.; Torres, T. Coord. Chem. Rev. 1999, 190-192, 231 and references therein.
26. Metal complexes [Zn(II) and Al(III)] of unsubstituted compound 2 have been described previously by one of us: Kudrik, E. V.; Islyaikin, M. K.; Smirnov, R. P. Zh. Org. Chim. 1997, 33, 1107. However, this is the first time that a free-base of this class of compounds, which we named thiadiazolephthalocyanines, is reported. Their electronic features are in good agreement with the 18 π-electron aromatic structure proposed for this system. The UV/vis spectrum of 2 (Figure 1) shows a group of bands in the visible range at 530, 564, and 615 nm, bathochromically shifted when compared with nonaromatic hemiporphyrazines. Therefore, compound 2 is electronically similar to the metalated complexes mentioned above and resembles its close relatives the triazolephthalocyanines: (a) Nicolau, M.; Cabezón, B.; Torres, T. Coord. Chem. Rev. 1999, 190-192, 231 and references therein.
27. (b) Nicolau, M.; Cabezón, B.; Torres, T. J. Org. Chem. 2001, 66, 89.
28. max 388 (3.73), 530 (sh), 564 (3.59), 615 nm (3.52).
29. max 265 (4.45), 328 (4.28), 428 (4.69), 452 (4.69), 515 (sh), 552 nm (3.73).
30. Analytical data were in agreement with the proposed structures.
31. The strong deshielding observed for the inner NH protons of 1 is noteworthy if compared with the chemical shifts exhibited by the corresponding pyrrolic protons of porphyrins and phthalocyanines. In these cases low-field shifts (-2 to -6 ppm) are observed owing to the diatropicity of the planar aromatic macrocycles. In contrast, values of ca. 14-15 ppm for the inner NH protons of nonplanar nonaromatic triazolehemiporphyrazines have been reported by us. See for example, ref 5c.
32. Since structural assignments could not be carried out from X-ray diffraction analysis because it was not possible to obtain appropriate single crystals of 1, a full optimization of the geometry was performed by a semiempirical quantum chemistry method (AM1). Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902.
33. Intramolecular hydrogen bonding of the inner NH groups has been found responsible for the observed nonplanarity of several macrocycles together with other factors such as core size, peripheral substituents, or crystal packing. See for example: (a) Vangberg, T.; Ghosh, A. J. Am. Chem. Soc. 1999, 121, 12154.
34. (b) Wondimagegn, T.; Ghosh, A. J. Phys. Chem. A 2000, 104, 4606.
35. (c) Wondimagegn, T.; Ghosh, A. J. Am. Chem. Soc. 2000, 122, 6375.
36. (d) Barkigia, K. M.; Chantranupong, L.; Smith, K. M.; Faker, J. J. Am. Chem. Soc. 1988, 110, 7566.
37. Senda, H.; Maruha, J. Acta Crystallogr. 1987, 43, 347.
38. Starova, G. L.; Frank-Kamenetskaya, O. V.; Makarskii, V. V.; Lopyrev, V. A. Kristallografiya 1980, 25, 1292.
39. In analogy to other hemiporphyrazines, lower homologues of compound 1 (namely "2 + 2" thiadiazolehemiporphyrazines) have been described as nonaromatic 20 π-electron conjugated systems consisting of two alterning subunits of isoindole and two 1,3,4-thiadiazole moieties, bound to each other through aza-bridges: (a) Kolesnikov, N. A.; Borodkin, V. F. Izv. Vyssh. Ucheb. Zaved., Khim., Khim. Tekhnol. 1972, 15, 880.
40. (b) Borodkin, V. F.; Kolesnikov, N. A.; Izv. Vyssh. Ucheb. Zaved., Khim., Khim. Tekhnol. 1970, 13, 738.
41. (c) Danilova, E. A.; Islyaikin, M. K.; Smirnov, R. P. Zh. Obshch. Khim. 1997, 67, 1376
42. (d) Danilova, E. A.; Islyaikin, M. K.; Borodkin, V. F. Izv. Vyssh. Ucheb. Zaved., Khim., Khim. Tekhnol. 1990, 33, 18. However, in light of the present Letter some of the conclusions drafted therein should be revised. Large non-porphyrinic macrocycles based on 1,3,4-thiadiazole have been reported by one of us.
43. (e) Kudrik, A. V.; Islyaikin, M. K., Smirnov, R. P. Zh. Obshch. Khim. 1996, 66, 1564.
44. (f) Kudrik, E. V.; Islyaikin, M. K.; Smirnov, R. P.; Kuzmitcenko, A. V. Russian Patent N 2134270.
45. max 251 (4.73), 365 (sh), 442 nm (4.07).
46. max 348 (4.49), 413 (sh), 475 nm (4.59).