Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 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.

PubMed Disclaimer

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

Similar articles

See all similar articles

Cited by

References

    1. Gouzerh P. Proust A. Chem. Rev. 1998;98:77–112. doi: 10.1021/cr960393d. - DOI - PubMed
    1. Rhule J. T. Hill C. L. Judd D. A. Schinazi R. F. Chem. Rev. 1998;98:327–358. doi: 10.1021/cr960396q. - DOI - PubMed
    1. Wang S.-S. Yang G.-Y. Chem. Rev. 2015;115:4893–4962. doi: 10.1021/cr500390v. - DOI - PubMed
    1. Kozhevnikov I. V. Chem. Rev. 1998;98:171–198. doi: 10.1021/cr960400y. - DOI - PubMed
    1. Proust A. Thouvenot R. Gouzerh P. Chem. Commun. 2008:1837–1852. doi: 10.1039/B715502F. - DOI - PubMed