Polyoxovanadate (POV) clusters are an important subclass of polyoxometalates with a broad range of molecular compositions and physicochemical properties. One relatively underdeveloped application of these polynuclear assemblies involves their use as atomically precise, homogenous molecular models for bulk metal oxides. Given the structural and electronic similarities of POVs and extended vanadium oxide materials, as well as the relative ease of modifying the homogenous congeners, investigation of the chemical and physical properties of pristine and modified cluster complexes presents a method toward understanding the influence of structural modifications (e.g. crystal structure/phase, chemical makeup of surface ligands, elemental dopants) on the properties of extended solids. This review summarises recent advances in the use of POV clusters as atomically precise models for bulk metal oxides, with particular focus on the assembly of vanadium oxide clusters and the consequences of altering the molecular composition of the assembly via organofunctionalization and the incorporation of elemental "dopants".
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