Molecular Design Strategy toward Diarylethenes That Photoswitch with Visible Light

Abstract

Photoactive molecules that reversibly switch upon visible light irradiation are one of the most attractive targets for biological as well as imaging applications. One possible approach to prepare such photoswitches is to extend π-conjugation length of molecules and shift the absorption bands to longer wavelengths. Although several attempts have been demonstrated based on this approach for diarylethene (DAE) photoswitches, photoreactivity of the DAE derivatives is dramatically suppressed when the conjugation length is extended by connecting aromatic dyes at the side positions of aryl groups in the DAE unit. In this study, we successfully prepared a visible-light reactive DAE derivative by introducing an aromatic dye at the reactive carbon atom of the DAE unit, optimizing orbital level of each component, and controlling the mutual orientation of the aromatic dye and the DAE unit. The DAE derivative (3) undergoes a photocyclization reaction upon irradiation with 560 nm light and the closed-isomer converts to the open-ring isomer upon irradiation with 405 nm light. The high photoconversion yields (>90%) were achieved for both photocyclization and photocycloreversion reactions. The photoreactivity induced by visible light irradiation and the molecular design strategy were discussed based on theoretical calculations.