Aqueous inorganic chemistry is central to many natural, anthropogenic and synthetic processes; and aqueous inorganic species in water span the size regime from simple ions, polynuclear metal-oxo clusters, nanoparticles and colloids, and finally infinite solids that self-assemble and precipitate. Our synthetic research focuses on all of these size regimes in the realm of transition metal and actinide polyoxometalates (POMs), as well as their related functional materials. We use these fascinating and beautiful clusters to understand the fundamentals of ion-pairing, electron transfer, and ion-exchange and sequestration in solution and at interfaces. Practical applications derived from our research include base-catalysis reactions, contaminant transport and separations, organization and separations in microbiological systems, nuclear fuel-cycle chemistries, and ion-transport in solid media