Mechanical Bond–Mediated Metal–Organic Polyhedra Elastomer

The integration of metal–organic polyhedra (MOPs) into polymers represents a promising strategy for engineering polymer materials with precise nanostructures, unlocking new avenues for high-end applications. However, achieving seamless integration between flexible, disordered polymer chains and rigid, structurally precise MOPs remains a formidable challenge. Herein, we report a class of MOP elastomers with mechanically interlocked structures as linking units, which endows the MOPs with good adaptability and stability in the polymer matrices, leading to a high-performance solid-state electrolyte material. This approach exploits multivalent coordination between the MOPs and pyridyl-based ligands to ensure molecular-level dispersion. Upon deformation, the resulting network activates a hierarchical energy dissipation pathway through host–guest dissociation, macrocycle sliding, and reversible metal–ligand rupture. Such an adaptive mechanism grants the material outstanding mechanical properties (fracture strength: 30.4 MPa, extensibility: 1450.6%, toughness: 247.1 MJ m–3), robust recoverability, and efficient thermal reprocessability. More importantly, it effectively protects the embedded MOPs, allowing them to retain structural integrity even under 500% strain or during hot-pressing. Furthermore, the anion-restraining ability of the MOPs, synergizing with the topological motion of the mechanical bonds, promotes Li-salt dissociation and facilitates rapid Li+ transport, enabling the material to function as a solid electrolyte with a room-temperature ionic conductivity of 1.82 × 10–4 S cm–1.