Programming Aggregation‐Induced Emission Luminogens into Vinyl Polymer Backbones via Macrocyclic Radical Ring‐Opening Copolymerization

Comprehensive Summary The incorporation of fluorophores into vinyl polymer backbones is highly desirable for developing advanced functional materials, yet remains a significant challenge due to the inert nature of the all‐carbon backbone. In this work, we present a versatile strategy to overcome this architectural limitation by directly integrating fluorophores into the vinyl polymer backbones. This is accomplished through the design and efficient synthesis of a novel macrocyclic monomer that incorporates tetraphenylethene (TPE), a well‐known aggregation‐induced emission (AIE) luminogen. Using photoinduced electron transfer–reversible addition–fragmentation chain transfer (PET‐RAFT) polymerization, we successfully demonstrated, for the first time, the effective incorporation of AIE units into vinyl polymer backbones. The polymerization proceeds in a controlled manner, as evidenced by first‐order kinetics and a linear increase in molecular weight with monomer conversion. This strategy is easily adaptable to a wide range of commercial vinyl monomers. The resulting polymers exhibit pronounced AIE behavior and can degrade under basic conditions. This methodology not only expands the synthetic toolbox for main‐chain functionalization but also provides a versatile platform for designing next‐generation vinyl polymers with inherent luminescent properties.