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

  • Dades identificatives

    Identificador: imarina:3654496
    Autors:
    Cai, WentingMorales-Martinez, RoserZhang, XingxingNajera, DanielRomero, Elkin LMetta-Magana, AlejandroRodriguez-Fortea, AntonioFortier, SkyeChen, NingPoblet, Josep MEchegoyen, Luis
    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- 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.
  • Altres:

    Autor segons l'article: 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
    Departament: Química Física i Inorgànica
    Autor/s de la URV: Morales Martínez, Roser / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
    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- 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.
    Àrees temàtiques: Química Materiais Interdisciplinar General chemistry Farmacia Ciências biológicas iii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Astronomia / física
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    Adreça de correu electrònic de l'autor: josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
    Identificador de l'autor: 0000-0002-4533-0623 0000-0001-5884-5629
    Data d'alta del registre: 2024-10-12
    Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
    Enllaç font original: https://pubs.rsc.org/en/content/articlelanding/2017/sc/c7sc01711a
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referència a l'article segons font original: Chemical Science. 8 (8): 5282-5290
    Referència 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 de l'article: 10.1039/c7sc01711a
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2017
    Tipus de publicació: Journal Publications
  • Paraules clau:

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