Tunable Aggregate-Induced Emissions and Supramolecular Self-Assembly of the Nanoclusters Based on Quaternary Ammonium AIEgen and Polyoxometalate.

Superstructures assembled by polyoxometalate (POM) clusters have attracted considerable attention due to their intriguing architectures and remarkable properties. The development of novel inorganic-organic hybrid materials exhibiting aggregation-induced emission (AIE) characteristics represents an important research direction. However, POM-based nanostructures that integrate both POM clusters and AIE luminogens (AIEgens) have rarely been reported in the literature. Herein, we designed and synthesized two POM-based hybrid materials, denoted as TPE-POM-1 and TPE-POM-2, through electrostatic self-assembly between tetraphenylethylene (TPE)-derived cationic AIEgens (TPE-1 and TPE-2) and Keggin-type silicotungstic acid (K4[α-SiW12O40]). The self-assembled morphologies and AIE properties of TPE-POM-1 and TPE-POM-2 were systematically investigated. The two AIEgen-modified POM clusters demonstrated remarkably enhanced AIE characteristics and controllable formation of diverse nanostructures, including layered and onion-like spherical micelles, free-standing films, and vesicular architectures in various solvent systems (tetrahydrofuran (THF)-water, THF-methanol, and chloroform-methanol). The proposed approach of this study presents a crucial design strategy for achieving precise control over the coassembly of POM-based hybrid materials with AIE characteristics through noncovalent interactions.