Photochromic, thermochromic, and fluorescent spirooxazines and naphthopyrans: a spectrokinetic and thermodynamic study.

The photochromic and thermochromic behavior of four commercially available Reversacol dyes are presented. The compounds studied belong to the class of spirooxazines and naphthopyrans, which are typically thermoreversible photochromic molecules. On stimulation with UV light, these compounds become colored and exhibit spectra which extend over the whole visible region. Increasing the temperature causes spontaneous coloration (thermochromism). Herein, absorption and fluorescence spectra, molar absorption coefficients of the colorless and colored forms, fluorescence and photochemical quantum yields, and kinetic parameters of thermal bleaching (rate constant, frequency factor, and activation energy) are determined in acetonitrile solution. The thermal ground-state reaction is exhaustively described in terms of thermodynamic parameters (equilibrium constant, free energy, enthalpy, and entropy). Temperature effects on photochemical and thermal colorabilities are evaluated. The results indicate that the two spirooxazines are good photochromes below room temperature, whereas they are efficient thermochromic compounds above room temperature. Naphthopyrans are better photochromes but worse thermochromic compounds than spirooxazines.