Rotational Isomerism, Electronic Structures, and Basicity Properties of "fully-Reduced" V14-type Heteropolyoxovanadates

Aleksandar Kondinski, Thomas Heine, Kirill Yu Monakhov

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17 Citations (Scopus)


We investigated computationally the α-, γ-, and β-isomeric structures, relative stabilities, and the electronic and basicity properties of magnetic [VIV14E8O50]12- (hereafter referred to as {V14E8}) heteropolyoxovanadates (heteroPOVs) and their heavier chalcogenide-substituted [VIV14E8O42X8]12- ({V14E8X8}) derivatives for E = SiIV, GeIV, and SnIV and X = S, Se, and Te. We used density functional theory (DFT) with scalar relativistic corrections in combination with the conductor-like screening model of solvation. The main purpose of this investigation is to introduce the structure-property relations in heteroPOVs as well as to assist the synthesis and molecular deposition of these molecular vanadium-oxide spin clusters on surfaces. "Fully-reduced" polyoxoanions {V14E8} and {V14E8X8} are virtually comprised of [VIV14O38]20- {V14} skeletons of different symmetries, that is, D2d for α-, D2 for γ-, and D4h for β-isomers, which are stabilized by the four {E2O3}2+ and four {E2OX2}2+ moieties, respectively. Our DFT calculations reveal stability trends α > γ > β for polyoxoanions {V14E8} and {V14E8X8}, based on relative energies and HOMO-LUMO energy gaps. The α-isomeric polyoxoanions {V14E8} and {V14E8X8} with the high negative net charges may easily pick up protons at the terminal E-Ot and E-Xt sites, respectively, which is evidenced by strongly negative enthalpies of monoprotonation. Energetically favorable sites on polyoxoanions α-{V14E8} and α-{V14E8X8} for electrostatic pairing with countercations were also determined. Among β and γ isomers, the hitherto unknown γ-[V14Sn8O50]12- and γ-[V14Sn8O42S8]12- seem to be the most viable targets for isolation. Furthermore, these Sn-substituted polyoxoanions are of high interest for electrochemical studies because of their capability to act as two-electron redox catalysts.

Original languageEnglish
Pages (from-to)3777-3788
Number of pages12
JournalInorganic Chemistry
Issue number8
Publication statusPublished - 2016 May 2

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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