Actinide-lanthanide single electron metal-metal bond formed in mixed-valence di-metallofullerenes
Yingjing Yan1,7, Laura Abella2,7, Rong Sun3,7, Yu-Hui Fang3, Yannick Roselló 2,Yi Shen1, Meihe Jin1, Antonio Rodríguez-Fortea2, Coen de Graaf2,4,Qingyu Meng1, Yang-Rong Yao1,5*（姚阳榕）, Luis Echegoyen6, Bing-Wu Wang3*（王炳武）,Song Gao3, Josep M. Poblet2* & Ning Chen1*(谌宁)
1College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University,
Suzhou, Jiangsu 215123, P. R. China.
2Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo 1, 43007 Tarragona, Spain.
3Beijing 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.
4ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain.
5Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, P. R. China.
6Department of Chemistry, University of Texas at El Paso,500 W University Avenue, El Paso, TX 79968, USA
Nature Communications,2023,14, 6637
Abstract：Understanding metal-metal bonding involving f-block elements has been a challenging goal in chemistry. Here we report a series of mixed-valence dimetallofullerenes, ThDy@C2n (2n =72, 76, 78, and 80) and ThY@C2n (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@D3h(5)-C78 shows a doublet as expected for an unpaired electron interacting with Y, and a SQUID magnetometric study of ThDy@D3h(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.