Shen Yi, Roselló Yannick, Abella Laura, Qiu Jiawei, Du Xiya, Meng Qingyu, Zheng Lihao, Cao Zhengkai, He Zhiwen, Poblet Josep M, Echegoyen Luis, Sun Lei, Rodríguez-Fortea Antonio, Chen Ning
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.
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo 1, 43007 Tarragona, Spain.
J Am Chem Soc. 2024 Dec 18;146(50):34924-34933. doi: 10.1021/jacs.4c14430. Epub 2024 Dec 7.
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, ThF@(7)-C and CaScF@(6)-C 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 Th@(7)-C hosts a σ Th-Th bond, an unprecedented actinide-actinide (Th-Th) single electron metal-metal bond is formed inside ThF@(7)-C upon the internal addition of fluoride. Similarly, while a Ca-Sc single electron bond exists in CaSc@(6)-C, 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.
内嵌富勒烯以其容纳含有独特键合模式的金属簇的非凡能力而闻名。在本研究中，我们报告了一种简便的策略来合成一类新的簇富勒烯，即氟化物簇富勒烯（FCF）。这项工作表明，锕系元素、稀土金属以及碱土金属可以被封装在各种富勒烯笼中，并且这些富勒烯可以以其原始形式获得，无需额外的功能化方法。值得注意的是，分离出了ThF@(7)-C和CaScF@(6)-C，并通过X射线单晶衍射、多种光谱技术以及密度泛函理论（DFT）计算对它们的分子结构和磁性进行了表征。这些发现表明，单个氟原子的独特内加显著改变了Th-Th和Ca-Sc的金属-金属键相互作用。虽然Th@(7)-C含有一个σ Th-Th键，但在内部添加氟化物后，在ThF@(7)-C内部形成了前所未有的锕系元素-锕系元素（Th-Th）单电子金属-金属键。同样，虽然在具有优异分子量子比特性质的CaSc@(6)-C中存在Ca-Sc单电子键，但添加氟化物会将该化合物转变为单重态。本研究不仅突出了成功合成了一类新型的FCF（这可能会是一个庞大的家族），还表明氟掺杂可以诱导新型的金属-金属键模式，从而导致潜在的有趣磁性。
