Author, as appears in the 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
Department: Química Física i Inorgànica
URV's Author/s: Morales Martínez, Roser / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
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- 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.
Thematic Areas: Química Materiais Interdisciplinar General chemistry Farmacia Ciências biológicas iii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
Author identifier: 0000-0002-4533-0623 0000-0001-5884-5629
Record's date: 2024-10-12
Papper version: info:eu-repo/semantics/publishedVersion
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Chemical Science. 8 (8): 5282-5290
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
Entity: Universitat Rovira i Virgili
Journal publication year: 2017
Publication Type: Journal Publications
Repositori URV