Author, as appears in the article.: Jimenez-Lozano, Pablo; Sole-Daura, Albert; Wipff, Georges; Poblet, Josep M.; Chaumont, Alain; Carbo, Jorge J.;
Department: Química Física i Inorgànica
URV's Author/s: Carbó Martin, Jorge Juan / Poblet Rius, Josep Maria / Solé Daura, Albert
Keywords: Polyoxometalates Dft
Abstract: The mechanism by which Zr-substituted and other transition metal-substituted polyoxometalates (POMs) form covalently linked dimers has been analyzed by means of static density functional theory (DFT) calculations with a continuous solvent model as well as Car-Parrinello molecular dynamics (CPMD) simulations with explicit solvent molecules. The study includes different stages of the process: the formation of the active species by alkalination of the solution and formation of intercluster linkages. CPMD simulations show that the Zr-triaqua precursor, [W5O18Zr(H2O)3]2-, under basic conditions, reacts with hydroxide anions to form Zr-aqua-hydroxo active species, [W5O18Zr(OH)(H2O)]3-. We computed the DFT potential energy profile for dimerization of [W5O18TM(OH)]n¿ [TM = ZrIV(H2O), ZrIV, TiIV, and WVI] anions. The resulting overall energy barrier is low for ZrIV, moderate for TiIV, and high for WVI. The computed thermodynamic balance favors the dibridged (¿OH)2 linkages for ZrIV, the monobridged (¿OH) linkage for TiIV, and the monomeric forms for WVI, in agreement with experimentally observed trends. The lowest energy barrier and largest coordination number of Zr-substituted POMs are both a consequence of the flexible coordination environment and larger radius of Zr.
Thematic Areas: Química Physical and theoretical chemistry Medicina i Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Engenharias iii Engenharias ii Engenharias i Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, inorganic & nuclear Chemistry (miscellaneous) Biotecnología Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: albert.soled@urv.cat j.carbo@urv.cat josepmaria.poblet@urv.cat
Author identifier: 0000-0002-3945-6721 0000-0002-4533-0623
Record's date: 2023-10-21
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: https://pubs.acs.org/doi/10.1021/acs.inorgchem.7b00096
Papper original source: Inorganic Chemistry. 56 (7): 4148-4156
APA: Jimenez-Lozano, Pablo; Sole-Daura, Albert; Wipff, Georges; Poblet, Josep M.; Chaumont, Alain; Carbo, Jorge J.; (2017). Assembly Mechanism of Zr-Containing and Other TM-Containing Polyoxometalates. Inorganic Chemistry, 56(7), 4148-4156. DOI: 10.1021/acs.inorgchem.7b00096
Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/
Article's DOI: 10.1021/acs.inorgchem.7b00096
Entity: Universitat Rovira i Virgili
Journal publication year: 2017
Publication Type: Journal Publications
Repositori URV