Fluorescence Switching and Photoisomerization of a Spiropyran Molecular Photoswitch through Confined Spaces Regulation in Crystals.

Abstract

Spiropyran (SP) and its derivatives are highly attractive owing to their distinctive merits in high contrast and fast response read-out systems. However, the realization of photoswitching properties of SP is hindered in the aggregate state, particularly in crystals owing to the dense packing of molecules leading to insufficient study of the relationship between the molecular structure/stacking mode and photoswitching behavior. Herein, we report three SP derivatives: different flexible chains (carboxyl group for SP-0 and ester group for SP-1) are attached to the indoline moiety, while the ester group is attached to the chromene moiety for SP-2. SP-1 exhibits fluorescent photoswitching properties in crystals due to the weak intermolecular interactions resulting in enough free space for the photoisomerization. The presence of hydrogen bonds in SP-0 enhances the molecular interactions to restrict the photoisomerization, and the ester group of SP-2 impacts the thermodynamic properties, thereby limiting the realization of photoswitching of SP-2.