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. 2020 Sep 11;10(56):33718-33730.
doi: 10.1039/d0ra05189f. eCollection 2020 Sep 10.

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

Soheila Mir  1 , Bahram Yadollahi  1 , Reza Omidyan  1 , Gholamhasan Azimi  1
Affiliations

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

Soheila Mir et al. RSC Adv. .

Abstract

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 H2O/OH-/O2- 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 [PW11O39(FeVO)]4-, possesses a high reactivity for oxygen transfer.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. The relevant numbering pattern of studied systems: (a) PW12, (b) PW11, (c) PWFen+ (n = 2, 3), (d) PWFen+OH2 (n = 2, 3 and 4) and (e) PWFen+O (n = 4, 5 and 6).
Fig. 1
Fig. 1. Energy level expressions of frontier molecular orbitals (FMOs) for (a) PW12 and (b) PW11 in the ground state. The orbital energy values have been represented in eV.
Fig. 2
Fig. 2. The optimized geometry of PWFeIIOH2 (a) in the singlet, (b) in the triplet and (c) in the quintet spin states obtained by OPTX-PBE/DZVP-GGA calculation.
Fig. 3
Fig. 3. The energy level expressions of frontier MOs for (a) PWFeII, (b) PWFeIIOH2, (c) PWFeIII and (d) PWFeIIIOH2 at ground state calculated at UOPBE/6-31G(d) level (LANL2DZ basis set on the metal atom). The orbital energy values have been represented in eV.
Fig. 4
Fig. 4. Unoccupied FeO π*-antibonding orbitals for high-oxidation states PWFeIV/V/VIO determined based on UOPBE/6-31G(d) level (LANL2DZ basis set on the metal atom).
Fig. 5
Fig. 5. The molecular orbitals expression of PWFeVO calculated at UOPBE/6-31G(d) (LANL2DZ basis set on the metal atom) level. The orbital energy values have been represented in eV.
See this image and copyright information in PMC

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