Polyoxovanadates (POVs), known for their wide applicability and relevance in chemical, physical and biological sciences, are a subclass of polyoxometalates and usually self-assemble in aqueous-phase, pH-controlled condensation reactions. Archetypical POVs such as the robust [VO42](12-) polyoxoanion can be structurally, electronically and magnetically altered by heavier group 14 and 15 elements to afford Si-, Ge-, As- or Sb-decorated POV structures (heteroPOVs). These main-group semimetals introduce specific chemically engineered functionalities which cause the generally hydrophilic heteroPOV compounds to exhibit interesting reactivity towards organic molecules, late transition metal and lanthanoid ions. The fully-oxidised (V(V)), mixed-valent (V(V)/V(IV) and V(IV)/V(III)), "fully-reduced" (V(IV)) and "highly-reduced" (V(III)) heteroPOVs possess a number of intriguing properties, ranging from catalytic to molecular magnet characteristics. Herein, we review key developments in the synthetic and structural chemistry as well as the reactivity of POVs functionalised with Si-, Ge-, As- or Sb-based heterogroups.

The non-covalent interactions between polyoxometalates and inorganic- and organic-based moieties give rise to functional nanoassemblies with diverse potential in applied science.

The sustainable development of IT-systems requires a quest for novel concepts to address further miniaturization, performance improvement, and energy efficiency of devices. The realization of these goals cannot be achieved without an appropriate functional material. Herein, we target the technologically important electron modification using single polyoxometalate (POM) molecules envisaged as smart successors of materials that are implemented in today's complementary metal-oxide-semiconductor (CMOS) technology. Lindqvist-type POMs were physisorbed on the Au(111) surface, preserving their structural and electronic characteristics. By applying an external voltage at room temperature, the valence state of the single POM molecule could be changed multiple times through the injection of up to 4 electrons. The molecular electrical conductivity is dependent on the number of vanadium 3d electrons, resulting in several discrete conduction states with increasing conductivity. This fundamentally important finding illustrates the far-reaching opportunities for POM molecules in the area of multiple-state resistive (memristive) switching.