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

Aleksandar Kondinski, Thomas Heine, Kirill Yu Monakhov

Research output: Contribution to journalArticlepeer-review

16 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

Funding Information:
A.K. thanks the Jacobs Univ. Bremen for providing financial support. K.Y.M. thanks the Deutsche Forschungsgemeinschaft for an Emmy Noether fellowship. The authors are also grateful to Dr. N. Vankova, Dr. L. Zhechkov, and Dr. P. Petkov for helpful discussions. This work was performed using the computational resources of the CLAMV (Computational Laboratories for Analysis, Modeling and Visualization) at Jacobs University Bremen.

Publisher Copyright:
© 2016 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


Dive into the research topics of 'Rotational Isomerism, Electronic Structures, and Basicity Properties of "fully-Reduced" V14-type Heteropolyoxovanadates'. Together they form a unique fingerprint.

Cite this