First steps in the inverse design of porous metal oxide materials: lacunary WellsDawson anion

Porous metal oxide materials have been obtained from a ring-shaped macrocyclic polyoxometalate structural building unit, [P8W48O184]40−. This is tungsten oxide building block with an integrated "pore" of 1 nm in diameter that, connected with transition metal linkers, is able to assemble zero to three-dimensional frameworks. Our investigation has been centered in the well-known [P2W18O62]6- Wells-Dawson structure, as well as its lacunary derivatives [P2W12O48]14-. Our aim is to predict new building blocks for ring-shaped porous material, hence we have constructed a few dozen different POMs, largely differing in their heteroatom (X) content, and have determined its electron densities, electronic and reduction/oxidation energies, and HOMO-LUMO gaps, the last of which gives at least tentative information surrounding the frameworks stability.