Interfacial Preparation of Polyoxometalate‐Based Hybrid Supramolecular Polymers by Orthogonal Self‐Assembly

Abstract The construction of organic–inorganic hybrid supramolecular polymers using polyoxometalate (POM) as building block is expected to bring new opportunities to the functionalization of supramolecular polymers and the development of novel POM‐based soft materials. Here, by using the orthogonal self‐assembly based on host–guest interactions and metal‐ligand interactions, we report the in situ construction of a novel POM‐based hybrid supramolecular polymer (POM‐SP) at the oil‐water interface, while the redox and competitive responsiveness can be triggered independently. Moreover, the binding energy of POM‐SP at the interface is sufficiently strong so that the assembly of POM‐SP jams, allowing the stabilization of liquids in nonequilibrium shapes, offering the possibility of fabricating all‐liquid constructs with reconfigurability.