Tungsten and Molybdenum Heteropolyanions with Different Central Ions—Correlation between Theory and Experiment

Density functional theory calculations were carried out to investigate the electronic structures of Keggin-typed [XMo(12)O(40)](n−) and [XW(12)O(40)](n−) anions with different heteroatoms (X = Zn(2+), B(3+), Al(3+), Ga(3+), Si(4+), Ge(4+), P(5+), As(5+), and S(6+)). The influence of solvent on redox properties of heteropolyanions was discussed. For [XW(12)O(40)](n−) systems two linear correlation: first, between the experimental redox potential and energies of LUMO orbital; and second, between the experimental redox potential and total energy interaction (calculated between internal tetrahedron (XO(4)(n−)), and rest of Kegging anion skeleton, (W(12)O(36))) were designated. Taking into account the similarity of XW(12)O(40)(n−) and XMo(12)O(40)(n−) systems (in geometry and electronic structure), the estimated redox potential of molybdenum heteropolyanions (with X being p block elements) in different solvent were proposed.