Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 11, Pages 3907-3915Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b10865
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Funding
- NSFC [51772196, 51772195]
- NSF of Jiangsu Province [BK20171211]
- Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
- project of scientific and technologic infrastructure of Suzhou [SZS201708]
- Spanish Ministry of Science [CTQ2017-87269-P]
- Generalitat de Catalunya [2013SGR199]
- ICREA foundation
- Spanish Ministry of Science
- U.S. National Science Foundation (NSF) under the NSF-PREM program [DMR 1205302, CHE-1408865]
- Robert A. Welch Foundation [AH-0033]
- Direct For Mathematical & Physical Scien
- Division Of Materials Research [1205302] Funding Source: National Science Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1408865] Funding Source: National Science Foundation
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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), U-2@C-80. 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 U-2@I-h(7)-C-80. In particular, the crystallographic data revealed that the U-U distance is within the range of 3.46-3.79 A, which is shorter than the 3.9 angstrom previously predicted for an elongated weak U-U bond inside the C-80 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, (I-h-C-80)(6-). Theoretical studies confirm the presence of a U-U bonding interaction and suggest that the weak U-U bond in U-2@I-h(7)-C-80 is strengthened upon reduction and weakened upon oxidation. The comprehensive characterization of U-2@I-h(7)-C-80 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.
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