Abstract
By means of the SCF MO LCAO method in the π-electronic (PPP) and all-valence (CNDO) approximations the electronic structures and spectral characteristics of the valence isomers of 2H-chromenes, thiochromenes, and 1,2-dihydroquinolines have been calculated. On the basis of a consideration of the electronic configuration of various excited states, an explanation has been given of the mechanism of the photochromism of the chromenes and their analogs. A hypothesis has been put forward concerning the possibility of thermochromism in 1,2-dihydronaphthalene. It has been shown that the diffuseness of the long-wave absorption band of the open forms of the compounds investigated is not connected with the existence of several stereoisomers. The influence of the heteroatom and of benzo-fusion on the long-wave absorption has been analyzed. The nature of the electronic transition responsible for the long-wave absorption of the photo-colored forms has been explained.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Literature cited
B. S. Lukyanov, M. I. Knyazhanskii, Yu. V. Revinskii, L. E. Nivorozhkin, and V. I. Minkin, Tetrahedron Lett., 2007 (1973).
R. S. Becker and J. Michl, J. Amer. Chem. Soc., 88, 5931 (1966).
J. Kolc and R. S. Becker, Photochem. Photobiol., 12, 383 (1970).
R. S. Becker and J. Kolc, J. Phys. Chem., 72, 997 (1968).
J. Kolc and R. S. Becker, J. Amer. Chem. Soc., 91, 6514 (1969).
J. Kolc and R. S. Becker, J. Amer. Soc., B, 17 (1972).
H. Kleinhuis, R. L. C. Wijting, and E. Havinga, Tetrahedron Lett., 255 (1971).
K. Salisbury, Tetrahedron Lett., 737 (1971).
R. Exelby and R. Grinter, Chem. Rev., 65, 247 (1965).
J. Koszar, Light-Sensitive Systems, Wiley, New York (1965).
J. A. Pople and D. L. Beveridge, Approximate Molecular Orbital Theory, McGraw Hill (1970).
K. Nichimoto and L. S. Forster, Theor. Chim. Acta, 4, 155 (1966).
V. I. Minkin, B. Ja. Simkin, and L. P. Olechnovich, Int. J. Sulf. Chem., 3A, No. 3 (1973).
R. Zahradnik, I. Tesarova, and J. Pancir, Collection Czech. Chem. Commun., 36, 2867 (1971).
J. Del Bene and H. H. Jaffe, J. Chem. Phys., 48, 1807 (1968); 49, 1221 (1968).
K. B. Wiberg, Tetrahedron, 24, 1083 (1968).
R. S. Becker, E. Dolan, and D. E. Balke, J. Chem. Phys., 50, 239 (1969).
T. Bercovici and E. Fischer, J. Amer. Chem. Soc., 86, 5687 (1964).
G. I. Lashkov and A. V. Shaplya, Opt. i Spektroskopiya, 21, 546 (1966).
N. W. Tyer and R. S. Becker, J. Amer. Chem. Soc., 92, 1295 (1970).
R. S. Mulliken and C. A. Rieke, Rep. Prog. Phys., 8, 231 (1941).
M. L. Bailey, Theor. Chim. Acta, 26, 87 (1972).
B. Tinland and C. Decoret, Tetrahedron Lett., 3019 (1971).
J. Iwai and J. Ide, Chem. Pharm. Bull. Japan, 10, 926 (1962).
B. Ya. Simkin, V. I. Minkin, and L. E. Nivorozhkin, Khim. Geterotsikl. Soedin., 76 (1974).
Author information
Authors and Affiliations
Additional information
For Communication III, see [1].
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 67–75, January, 1974.
Rights and permissions
About this article
Cite this article
Minkin, V.I., Simkin, B.Y., Nivorozhkin, L.E. et al. Photochromic and thermochromic spirans. Chem Heterocycl Compd 10, 59–66 (1974). https://doi.org/10.1007/BF00475910
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00475910