ThC2@C82versusTh@C84: unexpected formation of triangular thorium carbide cluster inside fullerenes

Shen, Yi; Yu, Xiaojuan; Meng, Qingyu; Yao, Yang-Rong; Autschbach, Jochen; Chen, Ning

doi:10.1039/d2sc04846a

ThC₂@C₈₂versusTh@C₈₄: unexpected formation of triangular thorium carbide cluster inside fullerenes

Journal Article · Thu Oct 20 00:00:00 EDT 2022 · Chemical Science

DOI:https://doi.org/10.1039/d2sc04846a· OSTI ID:1897278

^[1]; ^[2]; Meng, Qingyu ^[1]; ^[1]; ^[2]; ^[1]

Soochow University, Suzhou (China)
State Univ. of New York (SUNY), Buffalo, NY (United States)

Synthesis of the first thorium-containing clusterfullerenes, ThC₂@C_s(6)–C₈₂ and ThC₂@C₂(5)–C₈₂, is reported. These two novel actinide fullerene compounds were characterized by mass spectrometry, single-crystal X-ray diffraction crystallography, UV–vis–NIR spectroscopy, and theoretical calculations. Crystallographic studies reveal that the encapsulated ThC₂ clusters in both C_s(6)–C₈₂ and C₂(5)–C₈₂ feature a novel bonding structure with one thorium metal center connected by a C≡C unit, forming an isosceles triangular configuration, which has not been hitherto observed for endohedral fullerenes or for solid phase thorium carbides. Electronic structure calculations assign a formal electronic structure of [Th⁴⁺(C₂)^2-]²⁺@[C₈₂]^2-, with pronounced donation bonding from (C₂)^2- to Th⁴⁺, secondary backbonding from the fullerene to thorium and Th–C double bond character in both compounds. This work presents a new family of endohedral fullerenes, MC₂@C_2n-2, being unexpected isomers of MC_2n, and provides broader understanding of thorium bonding.

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Research Organization:: State Univ. of New York (SUNY), Albany, NY (United States)

Sponsoring Organization:: National Science Foundation of China; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001136

Other Award/Contract Number:: 91961109
52172051

OSTI ID:: 1897278

Alternate ID(s):: OSTI ID: 2419597

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 44 Vol. 13; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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