Photoactivation of Solid-State Fluorescence through Controllable Intermolecular [2+2] Photodimerization.

Intermolecular [2+2] photodimerization provides a distinctive approach to construct photoresponsive fluorescent materials in a manner of switching on solid-state fluorescence. Herein, we report efficient photoactivation of bright solid-state fluorescence based on controllable intermolecular [2+2] photodimerization reaction of benzo[b]thiophene 1,1-dioxide (BTO) derivatives, which provides a simple and effective way to construct smart photoresponsive solid-state fluorescent materials. Rational choice of substituent in BTO molecular skeleton enables them to efficiently undergo photodimerization through regulating molecular stacking in crystal, and also leads to photoactivation of solid-state fluorescence due to the generation of brightly fluorescent photodimers. This intermolecular photodimerization reaction also offers an effective method to synthesize photostable AIEgens with purely through-space conjugation.