Easily Accessible Substituted Heterocyclic Hemithioindigos as Bistable Molecular Photoswitches.

Abstract

Thioaurone chromophores, part of the indigoid family and commonly named hemithioindigos, have recently gained attention due to their interesting photoswitching properties. The study focuses on heterocyclic hemithioindigos (Het-HTIs) and investigates their synthesis using electron-rich and electron-poor heterocycles and modifications to the thioindigo moiety. Furthermore, it aims to evaluate the photoswitching performances of these synthesised compounds, with a particular emphasis on the influence of the heterocycles on the photoisomerization capabilities, which was found to be more prominent than the modifications made to the thioindigo moiety. Among the 44 Het-HTIs tested, several exhibited highly efficient photoswitchable properties, demonstrating Z-to-E photoisomerization in the blue region, and E-to-Z photoisomerization in the green or the red regions. Additionally, the metastable E-isomer displayed an impressive half-life of up to 54 days in a polar solvent (DMSO). These results suggest that heterocyclic hemithioindigos hold great promise as photoswitches for researchers interested in light-controlled molecular mechanisms.