Efficient Synthesis of Metastable Cyclodextrin‐Based Polyrotaxanes with Tunable Threading Ratios

Cyclodextrin‐based polyrotaxanes (CD‐PRs) are gaining attention for their dynamic sliding rings along the polymer axis, enabling various applications in molecular shuttles, drug delivery, and durable polymers with slidable cross‐links. However, the conventional synthesis of CD‐PRs with tunable threading ratios is typically laborious, time‐consuming, and complicated, which limits their scalability and cost‐effectiveness. Herein, we highlight the great potential of planetary centrifugal mixing, a process that significantly accelerates and simplifies the initial synthesis of polypseudorotaxanes (PPRs), followed by a thiol‐ene click reaction as an efficient end‐capping reaction for the synthesis of PRs. Notably, PRs synthesized with glutathione (GSH) as the end‐capping reagent are in a metastable state, where GSH act as a molecular bumper that significantly prevent de‐threading of α‐CD rings at room temperature. Moreover, the rate of ring de‐threading can be precisely controlled by heating, enabling the preparation of metastable PRs with tunable threading ratios over a wide range. The developed strategy is of great significance to the efficient synthesis of CD‐PRs, thus marking a significant step towards their practical application in advanced functional materials and devices.