Rigid Polymer Network-Based Autonomous Photoswitches Working in the Solid State Encoded by Room-Temperature Phosphorescence.

Autonomous molecular switches with self-recoverability are of great theoretical and experimental interest since they can avoid additional chemical or energy imposition during the working process. Due to the high energy barrier, however, the solid state is generally unfavorable for materials to exhibit the autonomous switch behavior. To promote the practical usage of the autonomous molecular switch, herein, we propose a prototype of an autonomous photoswitch that can work in the solid state based on a rigid polymer network. A hexacarboxylic sodium-modified hexathiobenzene compound was employed as a photoexcitation-driven unit, which can undergo molecular aggregation upon irradiation because of the distinct conformational difference between the ground state and the photoexcited state. Then, we selected a relatively rigid polymer named poly(dimethyldiallylammonium)chloride (PDDA) to complex with the hexacarboxylic sodium-modified hexathiobenzene through electrostatic coupling. Through optimization, the photoexcitation-controlled molecular aggregation and its self-recovery can work well in the solid matrix of PDDA under rhythmical photoirradiation. This process can be easily encoded by a self-recoverable room-temperature phosphorescence, featuring an excellent performance of the autonomous switch.