Issue 23, 2023

Th@C2(8)-C84 and Th@Cs(15)-C84: impact of actinide metal ions on the electronic structures of actinide endohedral metallofullerenes

Abstract

Two novel thorium-based endohedral metallofullerenes (EMFs), Th@C2(8)-C84 and Th@Cs(15)-C84, have been successfully synthesized and fully characterized by MALDI-TOF mass spectroscopy, single-crystal X-ray diffraction, UV-vis-NIR spectroscopy, cyclic voltammetry, and DFT computations. The molecular structures of Th@C2(8)-C84 and Th@Cs(15)-C84 were unambiguously determined by single-crystal X-ray crystallography, which differ from the previous theoretical prediction that the most stable structure among the Th@C84 isomers is Th@Cs(10)-C84. These results, together with the previous reports of the isomers of U@C84, show that the C2(8)-C84 cage can only be stabilized by the encapsulation of actinide metals (U and Th). Detailed structural analysis shows that, in these structures, the encapsulated actinide atom has a unique interaction with the sumanene-type hexagon, which likely contributes to the stabilization of the endohedral molecular structures. Moreover, the two thorium-based EMFs show UV-vis-NIR spectra and redox behaviors that are notably different from those of the previously reported U@C84 isomers with the same carbon cages, suggesting that, different from lanthanide-based EMFs, endohedral actinide metal atoms have an important impact on the electronic structures of actinide metallofullerenes.

Graphical abstract: Th@C2(8)-C84 and Th@Cs(15)-C84: impact of actinide metal ions on the electronic structures of actinide endohedral metallofullerenes

Supplementary files

Article information

Article type
Research Article
Submitted
30 Jun 2023
Accepted
04 Okt 2023
First published
07 Okt 2023

Inorg. Chem. Front., 2023,10, 6901-6908

Th@C2(8)-C84 and Th@Cs(15)-C84: impact of actinide metal ions on the electronic structures of actinide endohedral metallofullerenes

T. Cao, Q. Meng, Z. Fu, Y. Shen, Y. Yan, Q. Wang, B. Zhao, W. Wang, K. Merimi, A. Rodríguez-Fortea, Y. Yao and N. Chen, Inorg. Chem. Front., 2023, 10, 6901 DOI: 10.1039/D3QI01215H

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