Shape‐Memorable, Self‐Healable, Recyclable, and Full‐Color Emissive Ultralong Organic Phosphorescence Vitrimers with Exchangeable Covalent Bonds

Abstract Polymeric materials displaying ultralong organic phosphorescence (UOP) have drawn much attention in the fields of optoelectronics, bioimaging, and information encryption. However, it is challenging to realize polymeric UOP materials with variable mechanical strength, self‐healing, and superior processability. This work presents a low‐cost strategy to achieve polymeric UOP with full‐color‐emission (doping vitrimers with different phosphorescent emitters) by introducing exchangeable covalent cross‐linked bonds. These amorphous polymers show ultralong lifetimes up to 1.75 s under ambient conditions. Impressively, bright afterglow can be observed after soaking the different color films in water for 4 weeks. Furthermore, the polymeric UOP with exchangeable links exhibits self‐healable, recyclable, and shape memory features due to the dynamic covalent networks. These results outline a fundamental strategy to construct multifunctional polymers and pave a way to expanding polymeric phosphorescence materials and their applications.