Visible‐Light‐Sensitive Photoliquefiable Arylazoisoxazoles for the Solar Energy Conversion, Storage and Controlled‐Release of Heat at Room Temperature or Lower Temperatures

The photoswitchable molecular solar thermal (MOST) energy storage systems that are capable of exhibiting high energy storage densities suffer from poor cyclability, the use of less abundant UV light of the solar spectrum, or reduced charging/discharging rates and poor photoconversions in solid states. Herein, we have designed and readily synthesized a novel set of para‐thioalkyl substituted arylazoisoxazoles, that undergo high trans‐cis and cis‐trans photoconversions under visible light, and show fast charging/discharging and impressive cyclability. Remarkably, C6‐and C10‐thioalkyl chains permitted reversible solid‐liquid phase transition with the formation of cis‐enriched charged states by 400 nm light irradiation and trans‐enriched discharged states by 530 nm light at various temperatures (10‐35 oC). Their solid‐to‐liquid phase transitions enabled storage of the latent heat in addition to isomerization energies, resulting in the high net energy storage densities of 189‐196 J/g, which are substantially higher than that of many recently reported azobenzene‐based MOST compounds (100‐161 J/g). Using a high‐resolution infrared camera, we further demonstrated that a brief irradiation of green light can be employed to readily release the trapped photon energy as heat. Our results suggest that the arylazoisoxazole with C6‐thioalkyl chain at para‐position can serve as an effective and eco‐friendly photoliquefiable MOST material.