Luminescent core–shell nanoparticles (NPs) with crosslinked aggregation‐induced emission (AIE) core structures, which exhibited excellent emission independent of the dispersion state of the NPs, have been developed by a facile one‐pot method based on the self‐assembly of an amphiphilic block copolymer poly(PEGMA)‐b‐poly(DB3VT). Core–shell micelles with a poly(DB3VT) core were formed from poly(PEGMA)‐b‐poly(DB3VT) in tetrahydrofuran (THF)/H2O condition, and the crosslinked AIE‐based structure was selectively incorporated into the core by the Suzuki coupling reaction between poly(DB3VT) blocks and tetraphenylethylene (TPE)‐based coupling monomers at the same time. This method afforded a uniform NP with a crosslinked TPE‐based AIE core structure. The obtained NP exhibited excellent emission both in diluted solution and solid states. This result indicated that the formed TPE‐based AIE core structure was always aggregated regardless of NP dispersion owing to the crosslinking as we expected. The crosslinked TPE‐based AIE core structure, which was related to the emission property, was readily tuned by the selection and combination of coupling monomers in the Suzuki coupling reaction. By incorporating electron‐deficient units into the core, the emission color could be successfully tuned from yellow‐green to orange and red while maintaining the emission property independent of the state of the NP dispersion. These results demonstrated that NPs with the crosslinked AIE core structures are a promising luminescent material design motif to realize emission independent on molecular dispersion.

Aggregation‐induced emission (AIE)‐active nanoparticles (NPs) exhibiting multicolor fluorescence and high‐quantum yields independent of the environment are important for the further development of next‐generation smart fluorescent materials. In this work, AIE‐active amphiphilic block copolymers were designed and synthesized by RAFT polymerization of a brominated tetraphenylethene (TPE)‐containing acrylate (A‐TPE‐Br). The block copolymer exhibited typical AIE effects in selective solvents, which can be explained by hydrophobic TPE aggregated in the core during micelle formation. Luminescent core–shell NPs with a crosslinked AIE core (fixed structure) were synthesized by the Suzuki coupling reaction of the bromine groups of the assembled block copolymer and boronic acid compounds. The NPs composed of TPE/thiophene crosslinked core showed green emission in both diluted state and solid state, implying the ability to fluoresce regardless of environmental changes and molecular dispersion. Multicolor luminescent NPs capable of changing color from blue to red were synthesized by changing the coupling compounds, such as anthracene for electron‐rich units and benzothiadiazole for electron‐deficient units. The effects of the nature of the donor and acceptor, as well as their combination (TPE/donor/acceptor sequence), on the color and fluorescent intensity of the core crosslinked NPs in the nonpolar and polar solvents, and solid state, were investigated.

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