Issue 12, 2024

Th@C2(14)-C86 and Th@C3(18)-C86: two missing C86 isomers stabilized by the encapsulation of thorium

Abstract

Two missing cage isomers of C86 have been successfully stabilized by the encapsulation of the actinide ion Th. The two novel isomers of Th@C86 were synthesized using the arc-discharge method and characterized using mass spectrometry, single-crystal X-ray crystallography, UV-vis-NIR spectroscopy and DFT calculations. The molecular structures of the two isomers were unambiguously assigned to Th@C2(14)-C86 and Th@C3(18)-C86 by crystallographic analysis. Both of these cage isomers of C86 have been predicted by computational studies but have never been experimentally confirmed until now. DFT computation reveals that both Th@C2(14)-C86 and Th@C3(18)-C86 present closed-shell electronic configurations with formally Th(IV), consistent with other previously reported Th based mono-metallofullerenes. Th@C2(14)-C86 has emerged as the third lowest-energy isomer with significant predicted abundance at temperatures of fullerene formation. Th@C3(18)-C86, on the other hand, represents an unexpected isomer with low thermodynamic stability, but significant abundance. Its formation was further rationalized as a kinetically trapped intermediate obtained from the lowest-energy and abundant Th@C2(8)-C84, by a C2 insertion and a single Stone–Wales transformation. This study highlights the unique impact of actinides on the stabilization of fullerene cage isomers and also provides a more in-depth understanding into the stabilization mechanism of fullerene cage isomers.

Graphical abstract: Th@C2(14)-C86 and Th@C3(18)-C86: two missing C86 isomers stabilized by the encapsulation of thorium

Supplementary files

Article information

Article type
Research Article
Submitted
23 Feb 2024
Accepted
02 May 2024
First published
06 May 2024

Inorg. Chem. Front., 2024,11, 3578-3584

Th@C2(14)-C86 and Th@C3(18)-C86: two missing C86 isomers stabilized by the encapsulation of thorium

J. Qiu, L. Zheng, Y. Roselló, K. Merimi, Y. Yao, Z. Cao, Z. He, J. M. Poblet, A. Rodríguez-Fortea and N. Chen, Inorg. Chem. Front., 2024, 11, 3578 DOI: 10.1039/D4QI00487F

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