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, Luís Echegoyen, Bing‐Wu Wang, Song Gao, Josep M. Poblet, Ning Chen
Abstract
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 2 n (2 n = 72, 76, 78, and 80) and ThY@C 2 n (2 n = 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 3 h (5)-C 78 shows a doublet as expected for an unpaired electron interacting with Y, and a SQUID magnetometric study of ThDy@ D 3 h (5)-C 78 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.