THE INVESTIGATION ON ELECTRONIC PROPERTIES AND STABILITY OF POLYOXOMETALATES FUNCTIONALIZED BY ORGANOMETALLIC TITANIUM [CpTi · SiW9V3O40]4- BY DENSITY FUNCTIONAL THEORY

Abstract

The electronic structures of [ CpTi · SiW 9 V 3 O 40]4- constructed from Keggin–type polyoxometalates functionalized by CpTi 3+ group have been investigated by Density Functional Theory (DFT) methods. We discuss the relative stability affected by incorporating the CpTi 3+ group into the different sites of the [ SiW 9 V 3 O 40]7- framework on the basis of geometrical parameters, total bonding energies, fragment analysis and frontier molecular orbitals analysis. The calculated results indicated that the structure of the CpTi 3+ group coordinating to one terminal oxygen and two bridging oxygen atoms of the Keggin–type polyoxoanion (system a) is more stable than that to three bridging oxygen atoms (system b). In system a, Ti -Ob1, Ti -Ob2 and Ti - Ot1 are relatively shorter, and as result, it exhibits a more compact and nearly spherical structure of the well-known Keggin–type [ SiW 9 V 3 O 40]7-. Fragment analysis elucidates that there is deviation of ΔE B in systems a and b, which makes a significant contribution to the stability of system a. The stability of different isomeric forms of polyoxoanions appears to be a balance between the stabilizing ΔE O and ΔE E terms and the destabilizing ΔE P term. The relatively small energy differences (ΔE B = 4.26 eV ) between systems a and b arise directly from this balance. Frontier molecular orbitals analysis further confirms the stability order of systems a > b by the difference of the HOMO-LUMO energy gap.