Author, as appears in the article.: López X

Department: Química Física i Inorgànica

URV's Author/s: López Fernández, Javier

Keywords: Transition metals Redox properties Polyoxometalates Polyoxometalate Inorganic chemistry Electronic structure Density functional theory Computational chemistry Calculations

Abstract: © 2017 Walter de Gruyter GmbH, Berlin/Boston 2017. This publication reviews some relevant features related with the redox activity of two inorganic compounds: [XM12O40]q- (Keggin structure) and [X2M18O62]q- (Wells-Dawson structure). These are two well-known specimens of the vast Polyoxometalate (POM) family, which has been the subject of extensive experimental and theoretical research owing to their unmatched properties. In particular, their redox activity focus a great deal of attention from scientists due to their prospective related applications. POMs are habitually seen as 'electron sponges' since many of them accept several electrons without losing their chemical identity. This makes them excellent models to study mechanisms of electrochemical nature. Their redox properties depend on: (i) the type and number of transition metal atoms in the structure, (ii) the basicity of the first reduced species and, occasionally, of the fully oxidized species; (iii) the size of the molecule, (iv) the overall negative charge of the POM, and (v) the size of the central heteroatom. In the last years, important collaboration between the experimental and theoretical areas has been usual on the development of POM science. In the present chapter three of these synergies are highlighted: the influence of the internal heteroatom upon the redox potentials of Keggin anions; the dependence of the redox waves of Fe-substituted Wells-Dawson compounds with pH; and the role of electron delocalization and pairing in mixed-metal Mo/W Wells-Dawson compounds in their ability to accept electrons. In these three cases, a complete understanding of the problem would not have been possible without the mutual benefit of experimental and computational data.

Thematic Areas: Physics and astronomy (miscellaneous) Physics and astronomy (all) Multidisciplinary sciences Materials science (miscellaneous) Materials science (all) General physics and astronomy General materials science General chemistry Chemistry (miscellaneous) Chemistry (all)

licence for use: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 2365-659X

Author's mail: javier.lopez@urv.cat

Author identifier: 0000-0003-0322-6796

Record's date: 2023-07-31

Papper version: info:eu-repo/semantics/publishedVersion

Link to the original source: https://www.degruyter.com/view/journals/psr/2/11/article-20170137.xml

Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/

Papper original source: Physical Sciences Reviews. 2 (11):

APA: López X (2017). Effect of protonation, composition and isomerism on the redox properties and electron (de)localization of classical polyoxometalates. Physical Sciences Reviews, 2(11), -. DOI: 10.1515/psr-2017-0137

Article's DOI: 10.1515/psr-2017-0137

Entity: Universitat Rovira i Virgili

Journal publication year: 2017

Publication Type: Journal Publications