Self‐assembly Strategies Driven by Supramolecular <scp>RAFT</scp> Polymerization: Pseudorotaxanes and Nanosheets

Comprehensive Summary This study explores the use of supramolecular RAFT polymerization for the efficient synthesis of pseudorotaxanes and functional nanosheets through the host‐guest interaction between β‐cyclodextrin (β‐CD) and the chain transfer agent (CTA) S , S ’‐bis(α,α’‐dimethylacetic acid) trithiocarbonate (BDAAT). The formation of the β‐CD@BDAAT complex significantly improves the water solubility of the CTA, thereby increasing the polymerization rate for N , N ‐dimethylacrylamide (DMA) and generating well‐defined pseudorotaxane structure. In the process of aqueous polymerization‐induced self‐assembly (PISA), this supramolecular approach enables the rapid fabrication of functional nanosheets, reducing the required time from one week to just 5 h. The non‐covalent support provided by β‐CD is crucial for stabilizing the layered nanosheet assembly, while host‐guest competition experiments also demonstrate the tunability of the morphology of non‐covalently assembled structures. This study highlights the versatility of supramolecular RAFT polymerization, offering a promising strategy for the rapid and efficient production of complex nanostructures in aqueous media.