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 O ] and [XW O ] anions with different heteroatoms (X = Zn , B , Al , Ga , Si , Ge , P , As , and S ). The influence of solvent on redox properties of heteropolyanions was discussed. For [XW O ] 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 ), and rest of Kegging anion skeleton, (W O )) were designated. Taking into account the similarity of XW O and XMo O systems (in geometry and electronic structure), the estimated redox potential of molybdenum heteropolyanions (with X being p block elements) in different solvent were proposed.