Solvation effects on spirooxazine to merocyanine thermal reversion kinetics in acetonitrile–water binary mixtures

Abstract

AbstractIn solution, the photochromic molecule 5‐methoxyspiro[indole‐phenanthrolinoxazine] (SPO) is in equilibrium with its corresponding merocyanine open isomer. In pure acetonitrile, there is about 22.5% of the open form, whereas in acetonitrile–water binary solvents this proportion increases to more than 60% when the water molar fraction χ(H2O) is around 0.80. Irradiation in the visible range leads to a photobleached steady state in which the proportion of the merocyanine open isomer decreases significantly. When irradiation is switched off, a slow thermal reversion of the closed spirooxazine to the open merocyanine takes place until the initial equilibrium position is reached. Kinetic analysis of a whole set of relaxation curves recorded at various water contents was used to establish a model involving multiple equilibria between three merocyanines in different solvation states (solvated by acetonitrile, solvated by an acetonitrile–water complex and hydrated). Their relative proportions, which are dependent on the binary mixture composition, were determined, in addition to their corresponding visible spectra. Copyright © 2004 John Wiley & Sons, Ltd.