On the design of a planar oxo matrix for binding transition metals: a density functional approach

Density functional theory method is applied to investigate the geometry and electronic structure of a molecular system considered as a model of a metal±oxo surface. Vanadyl cation complexed by 2-hydroxyisonaphthalic acid is chosen as a building block, which gives an extended layer-type structure where planar, dimeric units are held together by a platinum or zirconium atom. The resulting two metal-linked two-dimer systems can be used as suitable model systems for polyoxomatrices, where the coordination around both platinum and zirconium atoms is square-planar. The electronic structures point out unpaired electrons which are responsible for magnetic interactions occurring mainly within isolated dimeric units for platinum system and with a more complicated spin distribution between adjacent dimers in the plane for zirconium system.