Articles producció científica> Química Física i Inorgànica

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

  • Datos identificativos

    Identificador: imarina:3654496
    Autores:
    Cai, WentingMorales-Martinez, RoserZhang, XingxingNajera, DanielRomero, Elkin LMetta-Magana, AlejandroRodriguez-Fortea, AntonioFortier, SkyeChen, NingPoblet, Josep MEchegoyen, Luis
    Resumen:
    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- C74(4 -) and U4+@C2(5)-C82(4-) . Surprisingly, the isomeric U@C2v(9)-C82 has a trivalent electronic configuration corresponding to U3+@C2v(9)-C82(3-) . 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.
  • Otros:

    Autor según el artículo: Cai, Wenting; Morales-Martinez, Roser; Zhang, Xingxing; Najera, Daniel; Romero, Elkin L; Metta-Magana, Alejandro; Rodriguez-Fortea, Antonio; Fortier, Skye; Chen, Ning; Poblet, Josep M; Echegoyen, Luis
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: Morales Martínez, Roser / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
    Resumen: 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- C74(4 -) and U4+@C2(5)-C82(4-) . Surprisingly, the isomeric U@C2v(9)-C82 has a trivalent electronic configuration corresponding to U3+@C2v(9)-C82(3-) . 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.
    Áreas temáticas: Química Materiais Interdisciplinar General chemistry Farmacia Ciências biológicas iii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) 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 antonio.rodriguezf@urv.cat
    Identificador del autor: 0000-0002-4533-0623 0000-0001-5884-5629
    Fecha de alta del registro: 2024-10-12
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    Enlace a la fuente original: https://pubs.rsc.org/en/content/articlelanding/2017/sc/c7sc01711a
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Chemical Science. 8 (8): 5282-5290
    Referencia de l'ítem segons les normes APA: Cai, Wenting; Morales-Martinez, Roser; Zhang, Xingxing; Najera, Daniel; Romero, Elkin L; Metta-Magana, Alejandro; Rodriguez-Fortea, Antonio; Fortier, (2017). Single crystal structures and theoretical calculations of uranium endohedral metallofullerenes (U@C-2n, 2n=74, 82) show cage isomer dependent oxidation states for U. Chemical Science, 8(8), 5282-5290. DOI: 10.1039/c7sc01711a
    DOI del artículo: 10.1039/c7sc01711a
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2017
    Tipo de publicación: Journal Publications
  • Palabras clave:

    Chemistry (Miscellaneous),Chemistry, Multidisciplinary
    Química
    Materiais
    Interdisciplinar
    General chemistry
    Farmacia
    Ciências biológicas iii
    Ciências biológicas i
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Astronomia / física
  • Documentos:

  • Cerca a google

    Search to google scholar