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

ABSTRACT

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,ß-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.