Controlled Synthesis of Topologically Diverse Polyrotaxanes by Ring-Opening Polymerization of Mechanically Interlocked Monomers

Mechanically interlocked polymers (MIPs) offer unconventional architectures that expand the design space of polymer chemistry, making them an emerging focus of polymer and supramolecular science. Yet their synthesis still lacks the precision and control established in conventional polymer chemistry. We report a living ring-opening polymerization that enables controlled construction of topologically diverse polyrotaxanes from two monomers—[2]catenanes and c[1]daisy chains. The method delivers main-chain and daisy-chain architectures with predictable molecular weights, narrow dispersities (Đ ≤ 1.13), and block copolymer access. Comparative studies reveal topology-dependent reactivity, underscoring the role of conformational constraints in polymerization kinetics. This unified route establishes a versatile platform for programmable MIP synthesis, bridging molecular topology with materials design and paving the way for next-generation mechanically bonded polymers.