Articles producció científica> Química Física i Inorgànica

When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky

  • Datos identificativos

    Identificador: imarina:9262518
    Autores:
    Laurans MMattera MSalles RK'Bidi LGouzerh PRenaudineau SVolatron FGuillemot GBlanchard SIzzet GSolé-Daura APoblet JMProust A
    Resumen:
    The mixed molybdenum/tungsten Keggin-type polyoxometalate (POM) hybrid (TBA)4[PW9Mo2O39{Sn(C6H4I)}] (TBA = tert-butylammonium) has been prepared by the reaction between [α-PW9Mo2O39]7- and [Cl3Sn(C6H4I)] in dried acetonitrile, in the presence of tetra-n-butylammonium bromide. A further coupling reaction affords the ferrocenyl derivative (TBA)4[PW9Mo2O39{Sn(C6H4)C≡C(C6H4)Fc}]. The POM hybrids have been thoroughly characterized by NMR and IR spectroscopies. Electrochemical analysis confirms their ease of reduction compared to the all-W analogue, albeit with a second reduction process occurring at a lower potential than in the all-Mo species. It is noteworthy that the second reduction is accompanied by an unusual red shift of the electronic absorption spectrum. Whereas there is no doubt that the first reduction deals with Mo, the location of the second electron in the bireduced species, on the second Mo or on W, has thus been the subject of a cross-investigation by spectroelectrochemistry, electron spin resonance, and theoretical calculations. Finally, it came out that the second reduction is also Mo-centered with two unpaired and antiferromagnetically coupled extra electrons.
  • Otros:

    Autor según el artículo: Laurans M; Mattera M; Salles R; K'Bidi L; Gouzerh P; Renaudineau S; Volatron F; Guillemot G; Blanchard S; Izzet G; Solé-Daura A; Poblet JM; Proust A
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: Poblet Rius, Josep Maria / Solé Daura, Albert
    Palabras clave: Molecular-orbital methods vibrational investigations redox potentials post-functionalization metal-oxide clusters magnetic-properties heteropoly blues electron delocalization charge-separation ab-initio calculation
    Resumen: The mixed molybdenum/tungsten Keggin-type polyoxometalate (POM) hybrid (TBA)4[PW9Mo2O39{Sn(C6H4I)}] (TBA = tert-butylammonium) has been prepared by the reaction between [α-PW9Mo2O39]7- and [Cl3Sn(C6H4I)] in dried acetonitrile, in the presence of tetra-n-butylammonium bromide. A further coupling reaction affords the ferrocenyl derivative (TBA)4[PW9Mo2O39{Sn(C6H4)C≡C(C6H4)Fc}]. The POM hybrids have been thoroughly characterized by NMR and IR spectroscopies. Electrochemical analysis confirms their ease of reduction compared to the all-W analogue, albeit with a second reduction process occurring at a lower potential than in the all-Mo species. It is noteworthy that the second reduction is accompanied by an unusual red shift of the electronic absorption spectrum. Whereas there is no doubt that the first reduction deals with Mo, the location of the second electron in the bireduced species, on the second Mo or on W, has thus been the subject of a cross-investigation by spectroelectrochemistry, electron spin resonance, and theoretical calculations. Finally, it came out that the second reduction is also Mo-centered with two unpaired and antiferromagnetically coupled extra electrons.
    Áreas temáticas: 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
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    Direcció de correo del autor: josepmaria.poblet@urv.cat
    Identificador del autor: 0000-0002-4533-0623
    Fecha de alta del registro: 2024-09-07
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Inorganic Chemistry. 61 (20): 7700-7709
    Referencia de l'ítem segons les normes APA: Laurans M; Mattera M; Salles R; K'Bidi L; Gouzerh P; Renaudineau S; Volatron F; Guillemot G; Blanchard S; Izzet G; Solé-Daura A; Poblet JM; Proust A (2022). When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky. Inorganic Chemistry, 61(20), 7700-7709. DOI: 10.1021/acs.inorgchem.2c00866
    DOI del artículo: 10.1021/acs.inorgchem.2c00866
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2022
    Tipo de publicación: Journal Publications
  • Palabras clave:

    Chemistry (Miscellaneous),Chemistry, Inorganic & Nuclear,Inorganic Chemistry,Physical and Theoretical Chemistry
    Molecular-orbital methods
    vibrational investigations
    redox potentials
    post-functionalization
    metal-oxide clusters
    magnetic-properties
    heteropoly blues
    electron delocalization
    charge-separation
    ab-initio calculation
    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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