AIE-Active Miktoarm Star Polymer Nanoassemblies: Structure-Dependent Self-Assembly and Photoluminescence Behavior

Abstract

Macromolecular architecture control of fluorescent polymers presents an important approach to diverse self-assembled nanostructures and tailored functions. Herein, tetraphenylethylene (TPE) derivatives with different bromopropionate and hydroxyl functionalities were synthesized efficiently. Based on the single electron transfer living radical polymerization (SET-LRP) of oligo(ethylene glycol) methyl ether acrylate (OEGA) and the mechanistic transition to reversible addition−fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA), well-defined aggregation-induced emission (AIE)-active miktoarm star TPE-(POEGA)n-(PBzMA)4-n (n = 1−3) nanoassemblies were synthesized for the first time. The nanoassemblies were utilized as an ideal platform to probe the intricate interplay between macromolecular architecture, self-assembly behavior, and fluorescence properties. Results showed that the arm engineering (changing the respective arm numbers) of miktoarm star polymers can bring about drastic alterations in the self-assembled morphology and photoluminescence characteristics. This arises from the influences of macromolecular structure on molecular packing, intermolecular interactions and intramolecular motions. This work highlights the unique advantage of miktoarm star architecture design and has far-reaching implications for the rational design of high-performance intelligent fluorescence systems.