Articles producció científica> Química Física i Inorgànica

Bicapped Keggin polyoxomolybdates: discrete species and experimental and theoretical investigations on the electronic delocalization in a chain compound

  • Identification data

    Identifier: imarina:6021016
    Authors:
    Salomon, WilliamRiviere, EricLopez, XavierSuaud, NicolasMialane, PierreHaouas, MohamedSaad, AliMarrot, JeromeDolbecq, Anne
    Abstract:
    Three monomeric polyoxometalates [M(C10H8N2)(3)][-PMoVI9MoV3O(40)Zn(2)(C10H8N2)(2)]2H(2)O (M-PMo12Zn2, M = Fe, Co, Ru) with {Zn(bpy)(2)}(2+) units capped on reduced -Keggin polyanions and [M(bpy)(3)](2+) counter-ions were synthesized under hydrothermal conditions. The 1D polymer [N(C4H9)(4)][Ru(C10H8N2)(3)][-PMoVI8MoV6O(43)] (Ru-PMo14) was prepared by a similar strategy, in the absence of 2,2-bpy ligands. In this chain capped reduced Keggin anions are linked via Mo-O-Mo bridges and are surrounded by both tetrabutylammonium cations and [Ru(bpy)(3)](2+) counter-ions. The compounds were characterized in the solid state by single crystal and powder X-ray diffraction and IR spectroscopy and in solution by P-31 NMR spectroscopy. P-31 diffusion ordered NMR spectroscopy (DOSY) indicates that the diffusion coefficient of the dissolved species of Ru-PMo14 corresponds to a dimeric structure. Magnetic susceptibility measurements performed on Ru-PMo14 show the existence of antiferromagnetic interactions between the d(1) electrons of the six Mo-V centers, with a singlet spin ground state. However, attempts to fit the data in the 2-300 K temperature range with Heisenberg Hamiltonians adapted for 0 or 1D systems suggest that these electrons are delocalized. Density Functional Theory (DFT) and Wave Function Theory (WFT) calculations indicate a migration of the electrons of the capping Mo-V centers into the PMo12 units at high temperature, allowing the rationalization of the experimental observations.
  • Others:

    Author, as appears in the article.: Salomon, William; Riviere, Eric; Lopez, Xavier; Suaud, Nicolas; Mialane, Pierre; Haouas, Mohamed; Saad, Ali; Marrot, Jerome; Dolbecq, Anne;
    Department: Química Física i Inorgànica
    URV's Author/s: López Fernández, Javier
    Keywords: State perturbation-theory Screening model Polyoxometalate-based materials Metal-complexes Implementation Hydrothermal syntheses Crystal-structures Coordination polymers Chemistry Building-blocks
    Abstract: Three monomeric polyoxometalates [M(C10H8N2)(3)][-PMoVI9MoV3O(40)Zn(2)(C10H8N2)(2)]2H(2)O (M-PMo12Zn2, M = Fe, Co, Ru) with {Zn(bpy)(2)}(2+) units capped on reduced -Keggin polyanions and [M(bpy)(3)](2+) counter-ions were synthesized under hydrothermal conditions. The 1D polymer [N(C4H9)(4)][Ru(C10H8N2)(3)][-PMoVI8MoV6O(43)] (Ru-PMo14) was prepared by a similar strategy, in the absence of 2,2-bpy ligands. In this chain capped reduced Keggin anions are linked via Mo-O-Mo bridges and are surrounded by both tetrabutylammonium cations and [Ru(bpy)(3)](2+) counter-ions. The compounds were characterized in the solid state by single crystal and powder X-ray diffraction and IR spectroscopy and in solution by P-31 NMR spectroscopy. P-31 diffusion ordered NMR spectroscopy (DOSY) indicates that the diffusion coefficient of the dissolved species of Ru-PMo14 corresponds to a dimeric structure. Magnetic susceptibility measurements performed on Ru-PMo14 show the existence of antiferromagnetic interactions between the d(1) electrons of the six Mo-V centers, with a singlet spin ground state. However, attempts to fit the data in the 2-300 K temperature range with Heisenberg Hamiltonians adapted for 0 or 1D systems suggest that these electrons are delocalized. Density Functional Theory (DFT) and Wave Function Theory (WFT) calculations indicate a migration of the electrons of the capping Mo-V centers into the PMo12 units at high temperature, allowing the rationalization of the experimental observations.
    Thematic Areas: Química Odontología Medicina ii Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Engenharias i Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Chemistry, inorganic & nuclear Biotecnología Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 14779226
    Author's mail: javier.lopez@urv.cat
    Author identifier: 0000-0003-0322-6796
    Record's date: 2024-09-07
    Papper version: info:eu-repo/semantics/acceptedVersion
    Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2018/dt/c8dt01313f#!divAbstract
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Dalton Transactions. 47 (31): 10636-10645
    APA: Salomon, William; Riviere, Eric; Lopez, Xavier; Suaud, Nicolas; Mialane, Pierre; Haouas, Mohamed; Saad, Ali; Marrot, Jerome; Dolbecq, Anne; (2018). Bicapped Keggin polyoxomolybdates: discrete species and experimental and theoretical investigations on the electronic delocalization in a chain compound. Dalton Transactions, 47(31), 10636-10645. DOI: 10.1039/c8dt01313f
    Article's DOI: 10.1039/c8dt01313f
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2018
    Publication Type: Journal Publications
  • Keywords:

    Chemistry, Inorganic & Nuclear,Inorganic Chemistry
    State perturbation-theory
    Screening model
    Polyoxometalate-based materials
    Metal-complexes
    Implementation
    Hydrothermal syntheses
    Crystal-structures
    Coordination polymers
    Chemistry
    Building-blocks
    Química
    Odontología
    Medicina ii
    Materiais
    Interdisciplinar
    Inorganic chemistry
    General medicine
    Farmacia
    Ensino
    Engenharias iv
    Engenharias iii
    Engenharias ii
    Engenharias i
    Ciências biológicas ii
    Ciências biológicas i
    Ciências ambientais
    Ciências agrárias i
    Chemistry, inorganic & nuclear
    Biotecnología
    Astronomia / física
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