Asymmetric Hybrid Polyoxometalates: A Platform for Multifunctional Redox‐Active Nanomaterials

Access to asymmetrically functionalised polyoxometalates is a grand challenge as it could lead to new molecular nanomaterials with multiple or modular functionality. Here, a simple “one-pot” synthetic approach to the isolation of an asymmetrically functionalised organic-inorganic hybrid Wells-Dawson polyoxometalate in good yield is presented. The cluster bears two organophosphonate moieties with contrasting physical properties: a chelating metal-binding group, and a long aliphatic chain unit that facilitates solvent-dependent selfassembly into soft nanostructures. The orthogonal properties of the modular system are effectively demonstrated by controlled assembly of POM-based redox-active nanoparticles. We propose that this simple, high-yielding synthetic method is a promising new approach to the preparation of multi-functional hybrid metal-oxide clusters, supermolecules and soft-nanomaterials