Taking classical polyoxometalates such as Lindqvist, Keggin, Dawson, and Preyssler anions as the starting point, a walk is taken through the electronic and structural properties of polyoxoanions in solution. We will discuss nucleation mechanisms, redox properties, and isomerism of polyoxometalates. The effects of confinement on water molecules and cation distributions inside nanocapsules are other topics discussed in the present review.

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