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Photochromic and thermochromic spirans

IX. Prediction of the stabilities of spiropyran structures and the electronic absorption spectra of their photocolored and thermocolored isomers

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Chemistry of Heterocyclic Compounds Aims and scope

Abstract

The self-consistent-field (SCF) molecular orbital (MO) Pariser-Parr-Pople (PPP) methods within the Dewar σ,π parametrization for the calculation of the properties of the ground states and variable β for the description of the excited states were used to estimate the relative stabilities of the spiropyran forms in spiranmerocyanine valence-tautomeric equilibria and to predict the electronic spectra of the photocolored and thermocolored forms of spirans. A correlation was found between the energies of anionic localization of the heterocation and the electron charge in the hypothetical position of spirocyclization and the experimental data on the stability of the spiropyran form. Another correlation links the calculated differences in the energies of the pyran and quinoneallide systems with the tendency of the latter to undergo cyclization. The stabilities of a large number of spiropyrans with different structures are predicted on the basis of the correlations obtained. The effect of various structural factors on the absorption spectra of the merocyanine forms of spiropyrans was studied. 2H-Naphtho[2,3-b]-pyran systems are recommended as promising photochromic compounds.

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Literature cited

  1. V. A. Anisimova, A. F. Pozharskii, L. E. Nivorozhkin, and V. I. Minkin, Khim. Geterotsikl. Soedin., No. 1, 108 (1978).

    Google Scholar 

  2. R. C. Bertelson, in: Photochromism (ed. by G. H. Brown), Wiley-Interscience, New York (1971), Chap. III, p. 45–432.

    Google Scholar 

  3. J. Koszar, Light-Sensitive Systems, Wiley, New York (1965), Chap. II.

    Google Scholar 

  4. V. A. Barachevskii, M. A. Gal'bershtam, Yu. E. Gerasimenko, and Yu. N. Gerulaitis, Zh. Vses. Khim. O-va., 19, 85 (1974).

    Google Scholar 

  5. E. Fischer, Fortschr. Chem. Forsch., 7, 605 (1967).

    Google Scholar 

  6. V. A. Barachevskii, Zh. Vses. Khim. O-va., 19, 423 (1974).

    Google Scholar 

  7. C. Schiele, M. Ruch, and D. Hendriks, Tetrahedron, 23, 3733 (1967).

    Google Scholar 

  8. E. B. Knott, J. Chem. Soc., 3038 (1951).

  9. V. P. Martynova, N. E. Shelepin, N. S. Loseva, É. R. Zakhs, L. E. Nivorozhkin, and V. I. Minkin, Khim. Geterotsikl. Soedin., No. 2, 167 (1971).

    Google Scholar 

  10. É. R. Zakhs, L. S. Éfros, and E. V. Bashut-skaya, Khim. Geterotsikl. Soedin., No. 11, 1580 (1973).

    Google Scholar 

  11. B. Ya. Simkin, V. I. Minkin, and L. E. Nivorozhkin, Khim. Geterotsikl. Soedin., No. 1, 76 (1974).

    Google Scholar 

  12. A. M. Samat, R. J. Guglielmetti, and G. J. Martin, Org. Magn. Res., 8, 62 (1976).

    Google Scholar 

  13. K. V. Veksler, É. R. Zakhs, V. M. Treiger, and L. S. Éfros, Khim. Geterotsikl. Soedin., No. 4, 447 (1971).

    Google Scholar 

  14. J. E. Lohr and C. Kortum, Ber. Bunsengesellsch., 70, 817 (1966).

    Google Scholar 

  15. N. E. Shelepin, Master's Dissertation, Rostov-on-Don (1972).

  16. N. D. Dmitrieva, I. L. Belaits, R. M. Liberzon, T. D. Platonova, and Yu. E. Gerasimenko, Zh. Org. Khim., 11, 1319 (1975).

    Google Scholar 

  17. É. R. Zakhs, V. P. Martynova, and L. S. Éfros, Khim. Geterotsikl. Soedin., No. 6, 750 (1974).

    Google Scholar 

  18. L. S. Éfros, É. R. Zakhs, and N. K. Beresneva, Khim. Geterotsikl. Soedin., No. 7, 1004 (1970); No. 7, 961 (1971).

    Google Scholar 

  19. N. A. Voloshin, N. E. Shelepin, and V. I. Minkin, USSR Inventor's Certificate No. 518491 (1976); Byul. Izobr., No. 23, 75 (1976).

  20. N. A. Voloshin, Master's Dissertation, Rostov-on-Don (1977).

  21. L. E. Nivorozhkin, N. S. Loseva, and V. I. Minkin, Khim. Geterotsikl. Soedin., No. 3, 318 (1972).

    Google Scholar 

  22. P. Appriou and R. J. Guglielmetti, Compt. Rend., 275C, 57, 1549 (1972).

    Google Scholar 

  23. P. Appriou, F. Garnier, and R. Guglielmetti, Helv. Chim. Acta, 58, 2563 (1975).

    Google Scholar 

  24. B. S. Luk'yanov, Yu. I. Ryabukhin, G. N. Dorofeenko, L. E. Nivorozhkin, and V. I. Minkin, Khim. Geterotsikl. Soedin., No. 2, 161 (1978).

    Google Scholar 

  25. K. Sato and M. Okazaki, J. Chem. Soc. Jpn., Chem. Ind. Chem., No. 12, 2146, 2150 (1975).

    Google Scholar 

  26. H. Baumann, Ann., 717, 124 (1968).

    Google Scholar 

  27. V. I. Minkin, V. A. Kosobut-skii, B. Ya. Simkin, Yu. A. Zhdanov, J. Mol. Struct., 24, 237 (1975).

    Google Scholar 

  28. É. R. Zakhs, E. V. Bashut-skaya, and L. S. Éfros, Khim. Geterotsikl. Soedin., No. 6, 818 (1976).

    Google Scholar 

  29. M. J. Dewar, Molecular Orbital Theory of Organic Chemistry, McGraw-Hill (1969).

  30. N. S. Loseva, L. E. Nivorozhkin, N. I. Borisenko, and V. I. Minkin, Khim. Geterotsikl. Soedin., No. 11, 1485 (1974).

    Google Scholar 

  31. V. I. Pantsyrnyi, M. A. Gal'bershtam, and N. A. Donskaya, Khim. Geterotsikl. Soedin., No. 5, 653 (1973).

    Google Scholar 

  32. M. B. Gordin and M. A. Gal'bershtam, Kinet. Katal., 12, 774 (1971).

    Google Scholar 

  33. E. Berman, R. E. Fox, and F. D. Thomson, J. Am. Chem. Soc., 81, 5605 (1959).

    Google Scholar 

  34. B. Ya. Simkin, V. I. Minkin, and V. A. Bren', Zh. Org. Khim., 13, 1910 (1977).

    Google Scholar 

  35. B. Tinland and C. Decoret, Gazz. Chim. Ital., 101, 792 (1971).

    Google Scholar 

  36. N. Tyutyulkov, S. Stoyanov, M. Taseva, and P. Schuster, J. Signal AM, 3, 435 (1975).

    Google Scholar 

  37. N. Mataga and K. Nishimoto, Z. Phys. Chem. (Frankfurt), 13, 140 (1957).

    Google Scholar 

  38. G. Arnold and G. Paal, Tetrahedron, 27, 1699 (1971).

    Google Scholar 

  39. V. I. Minkin, L. E. Nivorozhkin, N. S. Trofimova, Yu. V. Revinskii, M. I. Knyazhanskii, N. V. Volbushko, and B. Ya. Simkin, Zh. Org. Khim., 11, 828 (1975).

    Google Scholar 

  40. R. Exelby and R. Grinter, Chem. Rev., 65, 247 (1965).

    Google Scholar 

  41. É. R. Zakhs, L. A. Zvenigorodskaya, and L. S. Éfros, Khim. Geterotsikl. Soedin., No. 12, 1618 (1973).

    Google Scholar 

  42. Ya. N. Malkin, V. A. Kuz'min, G. G. Dyadyusha, A. N. Boguslavskaya, and F. A. Mikhailenko, Izv. Akad. Nauk SSSR, Ser. Khim., No. 3, 555 (1976).

    Google Scholar 

  43. A. I. Kiprianov, Usp. Khim., 40, 1283 (1971).

    Google Scholar 

  44. Ya. N. Malkin, V. A. Kuz'min, and F. A. Mikhailenko, Izv. Akad. Nauk SSSR, Ser. Khim., No. 1, 83 (1977).

    Google Scholar 

  45. R. S. Becker and J. Kolc, J. Phys. Chem., 72, 997 (1968).

    Google Scholar 

  46. V. I. Minkin, B. Ya. Simkin, L. P. Olekhnovich, and M. I. Knyazhanskii, Teor. Exp. Khim., 10, 668 (1974).

    Google Scholar 

  47. B. Ya. Simkin, V. I. Minkin, and V. I. Natanzon, Summaries of Papers Presented at the Sixth All-Union Conference on Quantum Chemistry [in Russian], Shtiintsa, Kishinev (1975), p. 157.

    Google Scholar 

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Authors and Affiliations

  1. Rostov State University, Scientific-Research Institute of Physical and Organic Chemistry, 344006, Rostov-on-Don

    B. Ya. Simkin, V. I. Minkin & L. E. Nivorozhkin

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  1. B. Ya. Simkin
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  2. V. I. Minkin
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  3. L. E. Nivorozhkin
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Additional information

See [1] for communication VIII.

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1180–1192, September, 1978.

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Simkin, B.Y., Minkin, V.I. & Nivorozhkin, L.E. Photochromic and thermochromic spirans. Chem Heterocycl Compd 14, 948–959 (1978). https://doi.org/10.1007/BF00509547

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  • DOI: https://doi.org/10.1007/BF00509547

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