Photoinduced Radical Persistent Luminescence in Semialiphatic Polyimide System with Temperature and Humidity Resistance

Organic persistent luminescence (pL) systems with photoresponsive dynamic features have valuable applications in the fields of data encryption, anticounterfeiting, and bioimaging. Photoinduced radical luminescent materials have a unique luminous mechanism with the potential to achieve dynamic pL. It is extremely challenging to obtain radical pL under ambient conditions; on account of it, it is unstable in air. Herein, a new semialiphatic polyimide‐based polymer (A0) is developed, which can achieve dynamic pL through reversible conversion of radical under photoexcitation. A “joint–donor–spacer–acceptor” molecular design strategy is applied to effectively modulate the intramolecular charge‐transfer and charge‐transfer complex interactions, resulting in effective protection of the radical generated under photoirradiation. Meanwhile, polyimide‐based polymers of A1–A4 are obtained by doping different amine‐containing fluorescent dyes to modulate the dynamic afterglow color from green to red via the triplet to singlet Förster resonance energy‐transfer pathway. Notably, benefiting from the structural characteristics of the polyimide‐based polymer, A0–A4 have excellent processability, thermal stability, and mechanical properties and can be applied directly in extreme environments such as high temperatures and humidity.