Visible light-induced switching of soft matter materials properties based on thioindigo photoswitches

Thioindigos are visible light responsive photoswitches with excellent spatial control over the conformational change between their *trans-* and *cis-* isomers. However, they possess limited solubility in all conventional organic solvents and polymers, hindering their application in soft matter materials. Herein, we introduce a strategy for the covalent insertion of thioindigo units into polymer main chains, enabling thioindigos to function within crosslinked polymeric hydrogels. We overcome their solubility issue by developing a thioindigo bismethacrylate linker able to undergo radical initiated thiol-ene reaction for step-growth polymerization, generating indigo-containing polymers. The optimal wavelength for the reversible *trans*/ *cis-* isomerisation of thioindigo was elucidated by constructing a detailed photochemical action plot of their switching efficiencies at a wide range of monochromatic wavelengths. Critically, indigo-containing polymers display significant photoswitching of the materials’ optical and physical properties in organic solvents and water. Furthermore, the photoswitching of thioindigo within crosslinked structures enables visible light induced modulation of the hydrogel stiffness. Both the thioindigo-containing hydrogels and photoswitching processes are non-toxic to cells, thus offering opportunities for advanced applications in soft matter materials and biology-related research.

Sarah L. Walden, Phuong H. D. Nguyen, Hao-Kai Li, Xiaogang Liu, Minh T. N. Le, Loh Xian Jun, Christopher Barner-Kowollik, Vinh X. Truong