Intrinsically Stretchable and Shape‐Memory Phosphorescent Polymers by Atom Transfer Radical Polymerization

Amorphous organic polymers with long-lived room-temperature phosphorescence (RTP) characteristics offer intriguing possibilities to advance information security, biological imaging, optoelectronic devices, and intelligent sensors. Despite the recent advances, access to phosphorescent polymers with excellent stretchability and shape memory performance remains a challenge. Herein, nanostructured RTP block copolymers biomimicking mussel cuticles were achieved by atom transfer radical polymerization (ATRP). The block copolymer retains the hard/soft two-phase morphology, affording excellent mechanical and shape memory performance. Additionally, this microphase-separated design effectively restricted the chromophore mobility and suppresses the nonradiative decay of triplet excitons, thus affording efficient RTP emission. This strategy is also compatible with other chromophores (from blue to red emission), enabling the block copolymers with controlled nanostructure, broad-spectrum emission, efficient RTP (lifetime up to 1000 ms), high stretchability (strain > 700%), and shape memory ability.