Cooperative photochemical reaction mechanism of femtosecond laser-induced photocoloration in spirooxazine microcrystals

Abstract

Microcrystalline powders of spirooxazine and spiropyran compounds do not show photocoloration under steady-state illumination, whereas they undergo photochromism on intense femtosecond laser-pulse excitation. We investigated the characteristic mechanism of the crystalline photochromism by studying the photocoloration of spironaphthooxazine (SNO) and its chlorosubstituted derivative (CI-SNO) with our femtosecond diffuse-reflectance spectroscopic system. In particular, femtosecond double-pulse excitation using 390+780-nm pulses and 390+ 390-nm pulses, with a variable time interval between the two pulses, was applied to reveal an intermediate species involved in the photocoloration. Although 780-nm excitation of an intermediate produced by 390-nm excitation did not lead to isomerization, the 390+390-nm excitation resulted in photocoloration. The yield for SNO decreased on increasing the interval from 40 ps to 5 ns, while that for CI-SNO was constant. The photocoloration mechanism in the crystalline phase is considered from the viewpoint of the time-dependent density of short-lived transient species, and it is concluded that cooperative interactions of excited states and nonplanar open forms play an important role in femtosecond laser-induced photochromism in these crystals. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.