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 chainend fidelity were confirmed by 1 H 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/H 2 O 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.

The construction of new macromolecular architecture is an effective route to obtain diverse self-assembled morphologies in polymerization-induced self-assembly (PISA). Herein, four macro-chain transfer agents (macro-CTAs) bearing three methoxy polyethylene glycol...