Fluoride Clusterfullerenes: Tuning Metal−Metal Bonding and Magnetic Properties via Single Fluorine Atom Doping
Yi Shen1,2, Yannick Roselló3, Laura Abella3, Jiawei Qiu1,2, Xiya Du4,5,6, Qingyu Meng1,2, Lihao Zheng1,2, Zhengkai Cao1,2, Zhiwen He1,2, Josep M. Poblet, Luis Echegoyen3, Lei Sun4,5,6,9, Antonio Rodríguez-Fortea3*, Ning Chen1,2*（谌宁）
1College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, P. R. China
2State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu 215123, P. R. China
3Departament de Química Física i Inorganica, Universitat Rovira i Virgili, 43007 Tarragona, Spain
4Department of Chemistry, School of Science, Westlake University, Hangzhou, Zhejiang 310030, China;
5Research Center for Industries of the Future, Westlake University, Hangzhou, Zhejiang 310030, China;
6Institute of Natural Sciences, Westlake Institute for Advanced Study, Hangzhou, Zhejiang 310024, China
7Department of Chemistry, University of Texas at El Paso, El Paso, Texas 79968, United States
8Institut Catala d’Investigació Química, 43007 Tarragona, Catalonia, Spain
9Key Laboratory for Quantum Materials of Zhejiang Province, Department of Physics, School of Science, Westlake University, Hangzhou, Zhejiang 310030, China
J. Am. Chem. Soc. 2024, 146, 34924−34933
Abstract: Endohedral fullerenes are known for their exceptional ability to host metal clusters that contain unique bonding motifs. In this study, we report a facile strategy to synthesize a new family of clusterfullerenes, fluoride clusterfullerenes (FCFs). This work demonstrates that actinides and rare earth metals as well as alkaline earth metals can be encapsulated within a variety of fullerene cages, and these fullerenes can be obtained in their pristine form without additional functionalization methods. Notably, Th2F@Ih(7)-C80 and CaScF@Cs(6)-C82 were isolated and their molecular structures and magnetic properties were characterized by X-ray single-crystal diffraction and multiple spectroscopic techniques as well as DFT calculations. These findings reveal that the unique internal addition of a single fluorine atom significantly alters the metal−metal bonding interactions of Th−Th and Ca−Sc. While Th2@Ih(7)-C80 hosts a σ2 Th−Th bond, an unprecedented actinide−actinide (Th−Th) single electron metal−metal bond is formed inside Th2F@Ih(7)-C80 upon the internal addition of fluoride. Similarly, while a Ca−Sc single electron bond exists in CaSc@Cs(6)-C82, which exhibits excellent molecular qubit properties, the addition of fluoride transforms the compound into a singlet. The present study not only highlights the successful synthesis of a novel family of FCFs, which will likely be an extensive family, it also shows that fluorine doping can induce novel metal−metal bonding motifs leading to potentially intriguing magnetic properties.
Link://pubs.acs.org/doi/10.1021/jacs.4c14430
