U-2@I-h(7)-C-80: Crystallographic Characterization of a Long-Sought Dimetallic Actinide Endohedral Fullerene

Identifier:  imarina:3669134

Handle: https://hdl.handle.net/20.500.11797/imarina3669134

Authors:  Zhang, XX; Wang, YF; Morales-Martínez, R; Zhong, J; de Graaf, C; Rodríguez-Fortea, A; Poblet, JM; Echegoyen, L; Feng, L; Chen, N

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.