Polylasso Network

Synthetic polymer networks face a fundamental trade-off: high energy dissipation and rapid recovery are mutually exclusive in conventional designs. Herein, inspired by the topological architecture of lasso peptides, we report the de novo synthesis of a polylasso network (PLN) that reconciles this long-standing conflict. Using a recognition-first interlocking-cyclization strategy, we construct stable lasso monomers that are subsequently cross-linked into a bulk network via thiol-ene click chemistry. The resulting topology establishes an intrinsic coupling between sliding-mediated high energy dissipation and entropy-driven rapid recovery. Under deformation, controlled tail sliding through the macrocyclic cavity, accompanied by host–guest dissociation and molecular friction, enables efficient energy dissipation, while geometric constraint limits excessive displacement and maintains structural integrity. Upon unloading, the elastic potential energy stored within the loop is rapidly released to drive tail retraction, while host–guest reassociation further promotes rapid restoration of the original lasso configuration and the overall network structure. Consequently, the PLN exhibits pronounced hysteretic energy dissipation (damping capacity, 90.2%) and rapid mechanical recovery under cyclic loading. These results establish molecular lasso topology as a general design principle for decoupling the conventional trade-off between energy dissipation and recovery, opening a route toward resilient soft materials with biological tissue-like mechanical adaptability.