Exploring Self-Assembly and the Self-Organization of Nanoscale Inorganic Polyoxometalate Clusters

Polyoxometalates (POMs) are a family of self-assembled molecular clusters with an unmatched range of physical properties, structural features, and sizes. The development of appropriate synthetic methodologies, analytical techniques, and approaches which allow the constructive exploration of the vast parameter space of POM chemistry is crucial for the understanding and control of the underlying complex reactions masked by the self-assembly. This chapter discusses the main aspects of the self-assembly that govern the POM-based chemical systems and the methodologies used for the generation of libraries of molecular synthons that can be used for the construction of large molecular moieties. We will illustrate how the effective combination of synthetic approaches in this area contributed to our deeper understanding of the self-assembly by revealing important mechanistic information. The final sections are devoted to discussing the self-organization of the preassembled molecular components into complex functional macrostructures.