DFT study of α-Keggin, lacunary Keggin, and iron(II–VI) substituted Keggin polyoxometalates: the effect of oxidation state and axial ligand on geometry, electronic structures and oxygen transfer

Herein, the geometry, electronic structure, Fe–ligand bonding nature and simulated IR spectrum of α-Keggin, lacunary Keggin, iron(ii/iii)-substituted and the important oxidized high-valent iron derivatives of Keggin type polyoxometalates have been studied using the density functional theory (DFT/OPTX-PBE) method and natural bond orbital (NBO) analysis. The effects of different Fe oxidation states (ii–vi) and H(2)O/OH(−)/O(2−) ligand interactions have been addressed concerning their geometry and electronic structures. It has been revealed that the d-atomic orbitals of Fe and 2p orbitals of polyoxometalate's oxygen-atoms contribute in ligand binding. Compared with other high valent species, the considered polyoxometalate system of [PW(11)O(39)(Fe(V)O)](4−), possesses a high reactivity for oxygen transfer.