Fine‐Tuning the Thermal Relaxation Dynamics of Indigo‐Based Photoswitches Using Selective Non‐Covalent Interactions Without Chemical Modification

Abstract Understanding the thermal relaxation dynamics of photoswitches is of crucial importance when considering application scenarios. Strategies for regulating the thermal relaxation rates of photoswitches have been mostly limited to modifying the chemical structures. Herein we demonstrate a complementary method of manipulating the thermal relaxation rate of indigo‐based photoswitches that does not require chemical modification. We used indigo‐based photoswitches in aprotic solvents as a model system to demonstrate this strategy. Our method creates a deactivated pathway that extends the thermal relaxation half‐life by selectively stabilizing the parent structure of the metastable Z ‐isomer via non‐covalent interaction. In addition, by establishing a quantitative kinetic model, we showed that controlling the strength of such selective stabilization enables fine‐tuning of the thermal relaxation rates to precisely access to targeted values.