Cytoskeleton‐Inspired Mechanically Interlocked Catenane Framework Enabling Robust yet Dynamic Polymer Networks

ABSTRACT The red blood cell cytoskeleton, featuring a highly ordered yet dynamically reconfigurable skeletal topology, offers an important structural inspiration for designing high‐performance polymeric materials that integrate mechanical robustness, structural stability, and dynamic adaptability. Inspired by this topology and functionality, we report a class of dynamic polymer networks featuring a continuous mechanically interlocked catenane framework ( CF MIN). The catenane framework is constructed via a sequential self‐assembly strategy, involving metal‐coordination‐driven formation of a supramolecular polyhexagonal network, followed by host–guest complexation with linear poly(crown ether). The resulting architecture integrates densely distributed mechanical bonds with a continuous rigid skeleton, thereby enabling simultaneous dynamic adaptability and structural stability. Compared with its structurally analogous but non‐interlocked control, CF MIN demonstrates significantly improved stiffness, strength, and toughness. These enhancements arise from hierarchical force‐triggered dynamic processes within catenane framework, involving host–guest dissociation, ring sliding, and metal–ligand bond rupture, together facilitating efficient energy dissipation. Meanwhile, topological constraints of catenane framework, along with robust metal coordination, impart superior structural stability to CF MIN, allowing network to retain integrity at temperatures up to 180°C. This work demonstrates that integrating mechanical bonds into ordered skeletal architectures offers a promising strategy for designing robust, dynamically adaptive, and thermally stable polymeric materials.