Precise Synthesis of Structurally Diverse Aggregation-Induced Emission-Active Polyacrylates by Cu(0)-Catalyzed SET-LRP with Macromolecular Structure-Correlated Emission

The rational design and precise synthesis of aggregation-induced emission (AIE) active polymers with diverse macromolecular structures are crucial to their applications in various fields. Herein, four tetraphenylethylene (TPE) bromopropionate initiators with the number of initiation sites of n = 1–4 were synthesized for the first time and applied in the Cu(0)-mediated single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate (MA) and tert-butyl acrylate (tBA). Well-controlled polymerization and high chain-end fidelity were confirmed by ¹H NMR and GPC. The produced polymers had diverse topology (linear/star) and the location of TPE moiety (chain-end/midchain/core), which were all precisely dictated by initiator structure. The macromolecular structure had a remarkable effect on the AIE properties of TPE-(PMA)_n in THF/H₂O mixtures and TPE-(PAA)_n (obtained after deprotecting tert-butyl groups from TPE-(PtBA)_n) in the B-R buffer solutions of different pH values. The fundamental insights gained into the macromolecular structure–AIE property correlation in our work are important for the design of AIE-active polymer-based functional materials.