Self‐Healing and Shape Memory Hypercrosslinked Metal‐Organic Polyhedra Polymers via Coordination Post‐Assembly

Abstract Coordination‐driven crosslinking networks with reversible and dynamic characteristics are gaining increasing interest in diverse application fields. Herein, we use a coordination crosslinking approach using metal‐organic polyhedra (MOPs) as high‐connectivity building blocks to post‐assemble a class of coordination hypercrosslinked MOP (CHMOP) polymers. The introduction of 12‐connected MOP nodes to the polymeric networks is critical to producing membranes that overcome the trade‐off between mechanical properties and dynamic healing, and meanwhile possess multifunctionalities including shape memory, solution processability, and 3D printing. The CHMOPs can also be used for anticorrosion coating and achieve function couplings, e.g., shape memory‐assisted self‐healing (SMASH), which have not been achieved in the MOP‐based hybrid materials yet. This work not only offers a feasible strategy to construct new multifunctional materials but also greatly expands the application scopes of MOPs.