Lindqvist-type polyoxometalates (POMs) are perhaps the most investigated metal-oxo clusters due to their compact structure, high symmetry, low molecular charge, and stability. As their early transition metal centres such as vanadium can exhibit several thermodynamically stable oxidation states, POMs containing these addenda atoms are able to accept and release multiple electrons without a significant change of their structure and stability. The possibility to address multiple charge states at one or several molecular centres opens the possibility to realize multistate logic, which offers significantly higher storage capacity per cell compared to binary logic. Thus, hybrid nanoelectronic devices involving POMs have the potential to revolutionize the current CMOS-based microelectronics. Another high-potential application area is batteries, which could reach immense cation densities immobilized in the POM vicinity. This was shown for electrode materials in lithium-ion batteries providing good ion diffusion and high discharge capacity. Both mentioned high potential applications require the POM to store charge locally, without leaking it to the environment, in particular not to ligands that immobilize the POM in the hybrid host structure. One of as yet unresolved questions remains what role do cations, that charge balance the POM structure, play in this fundamentally important charging / discharging process? Also, the interplay of counterions and ligand functionalities at POM in that respect has not been researched so far. Tailoring of these properties is, however, key to a variety of potential applications of switchable POMs, including multistate data storage, highsensitivity nanoscale sensing, rechargeable batteries, etc. The first experimental work investigating the structural characteristics, the reactivity against reduction and protonation, and the redox chemistry of Lindqvist-type V6O19based (POV6) structures [V V 6O13{(OCH2)3CR'}2] 2-(R' = NO2, CH2OH, Me) is that of Zubieta and co-workers, where the reduction and protonation of these tris(alkoxo) ligated complexess in solution were studied by simultaneous addition of electrons and cations.