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

Kondinski A, Heine T, Monakhov KY (2016)

Publication Type: Journal article

Publication year: 2016

Journal

Inorganic Chemistry American Chemical Society

Book Volume: 55

Pages Range: 3777-3788

Journal Issue: 8

DOI: 10.1021/acs.inorgchem.5b02636

Abstract

We investigated computationally the α-, γ-, and β-isomeric structures, relative stabilities, and the electronic and basicity properties of magnetic [V^IV14E8O50]^12- (hereafter referred to as {V14E8}) heteropolyoxovanadates (heteroPOVs) and their heavier chalcogenide-substituted [V^IV14E8O42X8]^12- ({V14E8X8}) derivatives for E = Si^IV, Ge^IV, and Sn^IV 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 [V^IV14O38]^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.

Involved external institutions

Jacobs University Bremen gGmbH

Germany (DE) Rheinisch-Westfälische Technische Hochschule (RWTH) Aachen

Germany (DE)

How to cite

APA:

Kondinski, A., Heine, T., & Monakhov, K.Y. (2016). Rotational Isomerism, Electronic Structures, and Basicity Properties of "fully-Reduced" V14-type Heteropolyoxovanadates. Inorganic Chemistry, 55(8), 3777-3788. https://doi.org/10.1021/acs.inorgchem.5b02636

MLA:

Kondinski, Aleksandar, Thomas Heine, and Kirill Yu Monakhov. "Rotational Isomerism, Electronic Structures, and Basicity Properties of "fully-Reduced" V14-type Heteropolyoxovanadates." Inorganic Chemistry 55.8 (2016): 3777-3788.

BibTeX: Download