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.

Control of Photomechanical Crystal Twisting by Illumination Direction.

Photomechanical molecular crystals have been investigated as mesoscopic photoactuators. Here, we report how the photomechanical twisting of 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene (1a) crystals depends on illumination direction. The ribbon-like crystal of 1a could be successfully prepared by a sublimation method. The ribbon crystal exhibited reversible photomechanical crystal twisting upon alternating irradiation with ultraviolet (UV) and visible light. Moreover, changing the UV illumination direction with respect to the crystal resulted in different twisting modes, ranging from helicoid to cylindrical. Control of photomechanical crystal deformation by illumination direction provides a convenient and useful way to generate a variety of photomechanical motions from a single crystal.