Articles producció científica> Química Física i Inorgànica

Assembly Mechanism of Zr-Containing and Other TM-Containing Polyoxometalates

  • Identification data

    Identifier: imarina:3650722
  • Authors:

    Jimenez-Lozano, Pablo
    Sole-Daura, Albert
    Wipff, Georges
    Poblet, Josep M.
    Chaumont, Alain
    Carbo, Jorge J.
    Inorganic Chemistry
    10.1021/acs.inorgchem.7b00096
    Inorganic Chemistry. 56 (7): 4148-4156
  • Others:

    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: josepmaria.poblet@urv.cat j.carbo@urv.cat
    Author identifier: 0000-0002-4533-0623 0000-0002-3945-6721
    Record's date: 2024-07-20
    Papper version: info:eu-repo/semantics/acceptedVersion
    Link to the original source: https://pubs.acs.org/doi/10.1021/acs.inorgchem.7b00096
    Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/
    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
    Article's DOI: 10.1021/acs.inorgchem.7b00096
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2017
    Publication Type: Journal Publications
  • Keywords:

    Chemistry (Miscellaneous),Chemistry, Inorganic & Nuclear,Inorganic Chemistry,Physical and Theoretical Chemistry
    Polyoxometalates
    Dft
    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
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