Reversible Surface Morphology Changes of a Photochromic Diarylethene Single Crystal by Photoirradiation

The surface morphology of a diarylethene single crystal [1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene] determined by atomic force microscopy changed reversibly upon photoirradiation. The crystal underwent a thermally irreversible but photochemically reversible color change (colorless to blue) upon alternate irradiation with ultraviolet (wavelength lambda = 366 nm) and visible (lambda > 500 nm) light that drove reversible photocyclization reactions. Upon irradiation with 366-nm light, new steps appeared on the (100) single-crystalline surface that disappeared upon irradiation with visible light (lambda > 500 nm). The step height, about 1 nm, corresponds to one molecular layer. Irradiation with 366-nm light formed valleys on the (010) surface that also disappeared by bleaching upon irradiation with visible light (lambda > 500 nm). The surface morphological changes can be explained by the molecular structural changes of diarylethenes regularly packed in the single crystal. These crystals could potentially be used as photodriven nanometer-scale actuators.