Density-functional theory (DFT) simulations 2 of fullyoxidized POV6 ligated by different tris(alkoxo) ligands (OCH2)3CR'' revealed that the position of the lowest unoccupied molecular orbital (LUMO), which is distributed between V atoms, is not considerably changed upon varying the type of the structurally exposed R'' group. Herewith the highest occupied molecular orbital (HOMO) energy differs for the various ligands.