Abstract
Activation energies have been measured for the thermal reactions in the formation and bleaching of colored forms of spiropyranes containing various heterocyclics as liquids, in the vitreous amorphous state, and in solution in benzophenone. The activation energies have been compared for thermal coloring, as have the quantum yields in the photocoloring, which are related to the spiropyrane structures. The thermal breakage of the Csp −O bond in a spiropyrane produces an unstable Bx isomer of the colored form. Nitrospiropyranes and spironaphthopyranes then give rise to the cis-cisoid isomer of the colored form produced in the photochemical reaction, which has an absorption spectrum close to that of the relatively stable colored form. The activation energy for the formation of the Bx form is usually correlated with the Csp −O bond length in the ground state, in contrast to the quantum yield.
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 4, pp. 476–480, July–August 1987.
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Kholmanskii, A.S., Veniaminova, G.I., Savina, E.V. et al. Structure dependence of the kinetic characteristics in spiropyrane thermochromism and photochromism. Theor Exp Chem 23, 446–450 (1988). https://doi.org/10.1007/BF00536366
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DOI: https://doi.org/10.1007/BF00536366