Photoreversible Birefringence Change of Diarylethene Single Crystals as Revealed by Change in Molecular Polarizability Anisotropy.

Stimuli-responsive organic crystals represent a new frontier of material chemistry. Recently, we have reported photoreversible interference color change to multicolor in single crystals composed of a photochromic diarylethene derivative, 1,2-bis(2-ethyl-5-phenyl-3-thienyl)perfluorocyclopentene (1a), accompanied by the photochromic reaction. The origin of the interference color change is due to the photoinduced birefringence change in the photoisomerization of diarylethenes. In this study, we newly found that single crystals composed of 1,2-bis(2,5-dimethyl-3-thienyl)perfluorocyclopentene (2a) also exhibit a photoreversible interference color change. The birefringence value for crystal 2a increased with the photocyclization conversion, while that for crystal 1a decreased. The relationship between the photoinduced birefringence changes for crystals 1a and 2a and their molecular structures was discussed based on the change in the molecular polarizability anisotropy accompanied by the photochromic reaction. These results would provide not only new opportunities for the application of photochromic crystals but also useful strategies for the design of crystalline materials that exhibit the desired birefringence change.