A Ligand‐Directed Spatial Regulation to Structural and Functional Tunability in Aggregation‐Induced Emission Luminogen‐Functionalized Organic–Inorganic Nanoassemblies

Abstract Aggregation‐induced emission luminogen (AIEgen)‐functionalized organic–inorganic hybrid nanoparticles (OINPs) are an emerging category of multifunctional nanomaterials with vast potential applications. The spatial arrangement and positioning of AIEgens and inorganic compounds in AIEgen‐functionalized OINPs determine the structures, properties, and functionalities of the self‐assembled nanomaterials. In this work, a facile and general emulsion self‐assembly tactic for synthesizing well‐defined AIEgen‐functionalized OINPs is proposed by coassembling alkane chain‐functionalized inorganic nanoparticles with hydrophobic organic AIEgens. As a proof of concept, the self‐assembly and structural evolution of plasmonic‐fluorescent hybrid nanoparticles (PFNPs) from concentric circle to core shell and then to Janus structures is demonstrated by using alkane chain‐modified AuNPs and AIEgens as building blocks. The spatial position of AuNPs in the signal nanocomposite is controlled by varying the alkane ligand length and density on the AuNP surface. The mechanism behind the formation of various PFNP nanostructures is also elucidated through experiments and theoretical simulation. The obtained PFNPs with diverse structures exhibit spatially tunable optical and photothermal properties for advanced applications in multicolor and multimode immunolabeling and photothermal sterilization. This work presents an innovative synthetic approach of constructing AIEgen‐functionalized OINPs with diverse structures, compositions, and functionalities, thereby championing the progressive development of these OINPs.