Various functional materials designed on the basis of polyoxometalates (POMs) inherit some structural and electronic features of their molecular precursors. Surprisingly, 99% of groups using POMs limit themselves by less than 1% of POMs described in the literature, namely Keggin and Dawson anions with non-metallic heteroatoms. Much wider variety of materials can be obtained if less popular and even exotic POMs are involved.
The following groups of POMs are considered: (i) less known heteropoly compounds, namely salts of Anderson and Dexter anions and decatungstates; (ii) difficult-to-synthesize keggin anions with metallic heteroatoms; (iii) isopoly compounds tending to complex pH-dependent equilibria in aqueous solutions, i.e .always coexisting with each other; (iv) mixed (W-Mo or W-V) isopoly compounds. Various routs to use these precursors for fabricating rechargeable materials and metal-oxide nanostructures are discussed and illustrated using the original experimental data on cathodic electrodeposition.

The following phenomena important for obtaining some certain material anions ls are accented: (i) adsorption of POMs on various electrode materials; (ii) association of multicharged POM and supporting cations; (iii) protonation of POMs; (iv) the specific features of electrochemical kinetics know for electroreduction of POMs. Carbon, platinum, gold and ITO supports are the most typical, but some data are related to mercury electrode involved for better understanding of kinetic details. The techniques applied to materials characterization are XRD, SEM, STM, IR spectroscopy, XPS and voltammetry.
This work is supported by RFBR, project No 05-03-32520a.

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