Asymmetric thiol-modified hybrid polyoxometalates: building blocks for hierarchical nanostructured redox materials

The development of hierarchical, redox-active nanostructures can drive new advances in fields ranging from energy storage to sensors and memristors. The self assembly of redox-active molecular building blocks into redox-active structures is especially promising, offering synthetic chemists the prospects of introducing unique chemical functionality into redox materials. In this contribution, we present an asymmetrically-functionalised organic-inorganic hybrid Wells-Dawson polyoxometalate bearing a chelating metal-binding group and a thiol-terminated aliphatic chain unit. The thiol-bearing group facilitates the solvent-dependent self-assembly of the cluster into soft nanostructures and grafting of the cluster onto Au surfaces and nanoparticles. We demonstrate how the redox properties of the molecular units are translated across the different classes of materials.