Diarylethene Photoswitches Undergoing 6π Azaelectrocyclic Reaction: Disrotatory Thermal Cycloreversion of the Closed-Ring Isomer

Abstract

Gaining insight into the dynamics of electrocyclic reactions is very important from both fundamental and application perspectives. In this study, we developed novel diarylethene photoswitches that undergo 6 azaelectrocyclic reaction. We found that they exhibit fast thermally reversible type (T-type) photochromism in contrast to the fact that common diarylethenes exhibit photochemically reversible type (P-type) photochromism. The quantum chemical calculations revealed that the fast T-type photochromism originates from the unprecedented disrotatory thermal cycloreversion of the closed-ring isomer. Our results provide useful information not only for the dynamics of the 6 azaelectrocyclic reaction but also for the further development of diarylethene photoswitches utilizing 6 azaelectrocyclic reaction.