Crystallographic Characterization of Er2C2@C80-88: Cluster Stretching with Cage Elongation

Shuaifeng Hu; Pei Zhao; Wangqiang Shen; Masahiro Ehara; Yunpeng Xie; Takeshi Akasaka; Xing Lu

doi:10.1021/acs.inorgchem.9b03269

Crystallographic Characterization of Er₂C₂@C_80-88: Cluster Stretching with Cage Elongation

Inorg Chem. 2020 Feb 3;59(3):1940-1946. doi: 10.1021/acs.inorgchem.9b03269. Epub 2020 Jan 21.

Authors

Shuaifeng Hu¹, Pei Zhao², Wangqiang Shen¹, Masahiro Ehara², Yunpeng Xie¹, Takeshi Akasaka¹, Xing Lu¹

Affiliations

¹ State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering , Huazhong University of Science and Technology , 1037 Luoyu Road , Wuhan 430074 , People's Republic of China.
² Research Center for Computational Science , Institute for Molecular Science , Okazaki 444-8585 , Japan.

PMID: 31961666
DOI: 10.1021/acs.inorgchem.9b03269

Abstract

Six dierbium carbide endohedral metallofullerenes have been synthesized and chromatographically isolated. Single-crystal X-ray diffractometry unambiguously ascertains their structures as Er₂C₂@C_2v(5)-C₈₀, Er₂C₂@C_s(6)-C₈₂, Er₂C₂@C_s(15)-C₈₄, Er₂C₂@C_2v(9)-C₈₆, Er₂C₂@C_s(15)-C₈₆, and Er₂C₂@C_s(32)-C₈₈, respectively. The Er···Er distances of the major erbium sites inside the C_s(6)-C₈₂, C_2v(5)-C₈₀, C_s(15)-C₈₄, C_s(15)-C₈₆, C_2v(9)-C₈₆, and C_s(32)-C₈₈ cages are 3.801, 3.860, 4.062, 4.066, 4.307, and 4.372 Å, respectively, which show a linear tendency with an increase in the major axis of the fullerene cages (8.064, 8.238, 8.508, 8.582, 8.815, and 8.953 Å, respectively). Furthermore, the electrochemical and molecular orbital analyses reveal that the redox chemistry of the Er₂C₂@C_80-88 isomers is associated with the carbon cage, which is different from the situations found for typical dimetallofullerenes, such as Y₂@C₈₂, Er₂@C_82-84, and Lu₂@C_82,86 isomers, which show metal-dependent oxidation processes, indicating the importance of C₂ insertion in carbide cluster metallofullerenes.