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

Abstract

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.