Articles producció científica> Química Física i Inorgànica

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

  • Identification data

    Identifier: PC:3386
    Authors:
    Poblet, JMLuis EchegoyenNing ChenRodriguez-Fortea, AWenting CaiRoser Morales-MartínezXingxing ZhangDaniel NajeraElkin L. RomeroAlejandro Metta-MagañaSkye Fortier
    Abstract:
    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.
  • Others:

    Author, as appears in the 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
    Department: Química Física i Inorgànica
    URV's Author/s: 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
    Abstract: 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.
    Research group: Química Quàntica
    Thematic Areas: Química Química Chemistry
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 2041-6520
    Author identifier: 0000-0002-4533-0623; ; ; 0000-0001-5884-5629; ; ; ; ; ; ;
    Record's date: 2019-01-14
    Last page: 5290
    Journal volume: 8
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2017/SC/C7SC01711A#!divAbstract
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Article's DOI: 10.1039/c7sc01711a
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2017
    First page: 5282
    Publication Type: Article Artículo Article
  • Keywords:

    Ful·lerens
    Química
    Química
    Chemistry
    2041-6520
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