Author, as appears in the article.: Zhang, Xingxing; Wang, Yaofeng; Morales-Martinez, Roser; Zhong, Jun; de Graaf, Coen; Rodriguez-Fortea, Antonio; Poblet, Josep M; Echegoyen, Luis; Feng, Lai; Chen, Ning
Department: Química Física i Inorgànica
URV's Author/s: De Graaf, Cornelis / Morales Martínez, Roser / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
Keywords: Fullerenes Electric arcs
Abstract: The nature of actinide-actinide bonds has attracted considerable attention for a long time, especially since recent theoretical studies suggest that triple and up to quintuple bonds should be possible, but little is known experimentally. Actinide-actinide bonds inside fullerene cages have also been proposed, but their existence has been debated intensively by theoreticians. Despite all the theoretical arguments, critical experimental data for a dimetallic actinide endohedral fullerene have never been obtained. Herein, we report the synthesis and isolation of a dimetallic actinide endohedral metallofullerene (EMF), U2@C80. This compound was fully characterized by mass spectrometry, single crystal X-ray crystallography, UV-vis-NIR spectroscopy, Raman spectroscopy, cyclic voltammetry, and X-ray absorption spectroscopy (XAS). The single crystal X-ray crystallographic analysis unambiguously assigned the molecular structure to U2@Ih(7)-C80. In particular, the crystallographic data revealed that the U-U distance is within the range of 3.46-3.79 Å, which is shorter than the 3.9 Å previously predicted for an elongated weak U-U bond inside the C80 cage. The XAS results reveal that the formal charge of the U atoms trapped inside the fullerene cage is +3, which agrees with the computational and crystallographic studies that assign a hexaanionic carbon cage, (Ih-C80)6-. Theoretical studies confirm the presence of a U-U bonding interaction and suggest that the weak U-U bond in U2@Ih(7)-C80 is strengthened upon reduction and weakened upon oxidation. The comprehensive characterization of U2@Ih(7)-C80 and the overall agreement between the experimental data and theoretical investigations provide experimental proof and deeper understanding for actinide metal-metal bonding interactions inside a fullerene cage.
Thematic Areas: Química Materiais Interdisciplinar General chemistry Farmacia Engenharias iv Engenharias iii Engenharias ii Colloid and surface chemistry Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biochemistry Astronomia / física
ISSN: 00027863
Author's mail: coen.degraaf@urv.cat josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
Author identifier: 0000-0001-8114-6658 0000-0002-4533-0623 0000-0001-5884-5629
Record's date: 2024-10-12
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: https://pubs.acs.org/doi/abs/10.1021/jacs.7b10865
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Journal Of The American Chemical Society. 140 (11): 3907-3915
APA: Zhang, Xingxing; Wang, Yaofeng; Morales-Martinez, Roser; Zhong, Jun; de Graaf, Coen; Rodriguez-Fortea, Antonio; Poblet, Josep M; Echegoyen, Luis; Feng (2018). U-2@I-h(7)-C-80: Crystallographic Characterization of a Long-Sought Dimetallic Actinide Endohedral Fullerene. Journal Of The American Chemical Society, 140(11), 3907-3915. DOI: 10.1021/jacs.7b10865
Article's DOI: 10.1021/jacs.7b10865
Entity: Universitat Rovira i Virgili
Journal publication year: 2018
Publication Type: Journal Publications
Repositori URV