Molecular Twisting Affects the Solid‐State Photochemical Reactions of Unsaturated Ketones and the Photomechanical Effects of Molecular Crystals.

Three groups of chalcone derivatives and their analogues involving halogen atoms (X=F, Cl, Br) have been synthesized. Firstly, the nearly planar acyclic chalcone derivatives were inclined to undergo photo‐induced stereospecific [2+2] cycloaddition, which triggered the crystals to exhibit macroscopic motions of bending or cracking. In particular, the single‐crystal‐to‐single‐crystal transformation happened upon UV irradiation of the crystals, which was helpful for the understanding photomechanical effects. Cyclic 3,4‐dihydronaphthalene‐based chalcone analogues possess a more twisted conformation, and they tend to undergo trans‐cis isomerization. No photomechanical effect was observed for the crystals of the cyclic chalcone analogues due to the lower isomerization rate. The twist degree of chroman‐based molecules was in between of the first two, [2+2] cycloaddition and trans‐cis isomerization simultaneously took place in crystals. Photo‐induced bending and twisting were observed for the crystals of chroman‐based chalcone analogues. Therefore, the differences in molecular dihedral angles in α,β‐unsaturated ketones were responsible for their photochemical characters and in turn to tune the photomechanical effects. In this work, a bridge between the molecular structures and solid‐state photochemical reactions triggered photomechanical crystals is built. [ABSTRACT FROM AUTHOR]