Actinide-lanthanide single electron metal-metal bond formed in mixed-valence di-metallofullerenes

Yingjing Yan; Laura Abella; Rong Sun; Yu-Hui Fang; Yannick Roselló; Yi Shen; Meihe Jin; Antonio Rodríguez-Fortea; Coen de Graaf; Qingyu Meng; Yang-Rong Yao; Luis Echegoyen; Bing-Wu Wang; Song Gao; Josep M Poblet; Ning Chen

doi:10.1038/s41467-023-42165-x

Actinide-lanthanide single electron metal-metal bond formed in mixed-valence di-metallofullerenes

Nat Commun. 2023 Oct 20;14(1):6637. doi: 10.1038/s41467-023-42165-x.

Authors

Yingjing Yan^#¹, Laura Abella^#², Rong Sun^#³, Yu-Hui Fang³, Yannick Roselló², Yi Shen¹, Meihe Jin¹, Antonio Rodríguez-Fortea², Coen de Graaf^{2

4}, Qingyu Meng¹, Yang-Rong Yao^{5

6}, Luis Echegoyen⁷, Bing-Wu Wang⁸, Song Gao³, Josep M Poblet⁹, Ning Chen¹⁰

Affiliations

¹ College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu, 215123, P. R. China.
² Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo 1, 43007, Tarragona, Spain.
³ Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Material Chemistry and Application, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China.
⁴ ICREA, Pg. Lluís Companys 23, 08010, Barcelona, Spain.
⁵ College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu, 215123, P. R. China. yryao@ustc.edu.cn.
⁶ Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, 230026, P. R. China. yryao@ustc.edu.cn.
⁷ Department of Chemistry, University of Texas at El Paso, 500 W University Avenue, El Paso, TX, 79968, USA.
⁸ Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Material Chemistry and Application, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China. wangbw@pku.edu.cn.
⁹ Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo 1, 43007, Tarragona, Spain. josepmaria.poblet@urv.cat.
¹⁰ College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu, 215123, P. R. China. chenning@suda.edu.cn.

^# Contributed equally.

Abstract

Understanding metal-metal bonding involving f-block elements has been a challenging goal in chemistry. Here we report a series of mixed-valence di-metallofullerenes, ThDy@C_2n (2n = 72, 76, 78, and 80) and ThY@C_2n (2n = 72 and 78), which feature single electron actinide-lanthanide metal-metal bonds, characterized by structural, spectroscopic and computational methods. Crystallographic characterization unambiguously confirmed that Th and Y or Dy are encapsulated inside variably sized fullerene carbon cages. The ESR study of ThY@D_3h(5)-C₇₈ shows a doublet as expected for an unpaired electron interacting with Y, and a SQUID magnetometric study of ThDy@D_3h(5)-C₇₈ reveals a high-spin ground state for the whole molecule. Theoretical studies further confirm the presence of a single-electron bonding interaction between Y or Dy and Th, due to a significant overlap between hybrid spd orbitals of the two metals.

Abstract

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