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Single crystal structures and theoretical calculations of uranium endohedral metallofullerenes (U@C2n, 2n = 74, 82) show cage isomer dependent oxidation states for U

  • Dades identificatives

    Identificador: PC:3386
    Autors:
    Poblet, JMLuis EchegoyenNing ChenRodriguez-Fortea, AWenting CaiRoser Morales-MartínezXingxing ZhangDaniel NajeraElkin L. RomeroAlejandro Metta-MagañaSkye Fortier
    Resum:
    Charge transfer is a general phenomenon observed for all endohedral mono-metallofullerenes. Since the detection of the first endohedral metallofullerene (EMF), La@C82, in 1991, it has always been observed that the oxidation state of a given encapsulated metal is always the same, regardless of the cage size. No crystallographic data exist for any early actinide endohedrals and little is known about the oxidation states for the few compounds that have been reported. Here we report the X-ray structures of three uranium metallofullerenes, U@D3h-C74, U@C2(5)-C82 and U@C2v(9)-C82, and provide theoretical evidence for cage isomer dependent charge transfer states for U. Results from DFT calculations show that U@D3h-C74 and U@C2(5)-C82 have tetravalent electronic configurations corresponding to U4+@D3h-C744− and U4+@C2(5)-C824−. Surprisingly, the isomeric U@C2v(9)-C82 has a trivalent electronic configuration corresponding to U3+@C2v(9)-C823−. These are the first X-ray crystallographic structures of uranium EMFs and this is first observation of metal oxidation state dependence on carbon cage isomerism for mono-EMFs.
  • Altres:

    Autor segons l'article: Poblet, JM; Luis Echegoyen; Ning Chen; Rodriguez-Fortea, A; Wenting Cai; Roser Morales-Martínez; Xingxing Zhang; Daniel Najera; Elkin L. Romero; Alejandro Metta-Magaña; Skye Fortier
    Departament: Química Física i Inorgànica
    Autor/s de la URV: POBLET RIUS, JOSEP MARIA; Luis Echegoyen; Ning Chen; RODRÍGUEZ FORTEA, ANTONIO; Wenting Cai; Roser Morales-Martínez; Xingxing Zhang; Daniel Najera; Elkin L. Romero; Alejandro Metta-Magaña; Skye Fortier
    Resum: Charge transfer is a general phenomenon observed for all endohedral mono-metallofullerenes. Since the detection of the first endohedral metallofullerene (EMF), La@C82, in 1991, it has always been observed that the oxidation state of a given encapsulated metal is always the same, regardless of the cage size. No crystallographic data exist for any early actinide endohedrals and little is known about the oxidation states for the few compounds that have been reported. Here we report the X-ray structures of three uranium metallofullerenes, U@D3h-C74, U@C2(5)-C82 and U@C2v(9)-C82, and provide theoretical evidence for cage isomer dependent charge transfer states for U. Results from DFT calculations show that U@D3h-C74 and U@C2(5)-C82 have tetravalent electronic configurations corresponding to U4+@D3h-C744− and U4+@C2(5)-C824−. Surprisingly, the isomeric U@C2v(9)-C82 has a trivalent electronic configuration corresponding to U3+@C2v(9)-C823−. These are the first X-ray crystallographic structures of uranium EMFs and this is first observation of metal oxidation state dependence on carbon cage isomerism for mono-EMFs.
    Grup de recerca: Química Quàntica
    Àrees temàtiques: Química Química Chemistry
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 2041-6520
    Identificador de l'autor: 0000-0002-4533-0623; ; ; 0000-0001-5884-5629; ; ; ; ; ; ;
    Data d'alta del registre: 2019-01-14
    Pàgina final: 5290
    Volum de revista: 8
    Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
    Enllaç font original: https://pubs.rsc.org/en/content/articlelanding/2017/SC/C7SC01711A#!divAbstract
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    DOI de l'article: 10.1039/c7sc01711a
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2017
    Pàgina inicial: 5282
    Tipus de publicació: Article Artículo Article
  • Paraules clau:

    Ful·lerens
    Química
    Química
    Chemistry
    2041-6520
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