Meng Qingyu, Morales-Martínez Roser, Zhuang Jiaxin, Yao Yang-Rong, Wang Yaofeng, Feng Lai, Poblet Josep M, 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.
Department de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel·lí Domingo 1, 43007 Tarragona, Spain.
Inorg Chem. 2021 Aug 2;60(15):11496-11502. doi: 10.1021/acs.inorgchem.1c01496. Epub 2021 Jul 18.
Actinide endohedral fullerenes have demonstrated remarkably different physicochemical properties compared to their lanthanide analogues. In this work, two novel isomers of Th@C were successfully synthesized, isolated, and fully characterized by mass spectrometry, X-ray single crystallography, UV-vis-NIR spectroscopy, Raman spectroscopy, and cyclic voltammetry. The molecular structures of the two isomers were determined unambiguously as Th@(9)-C and Th@(5)-C by single-crystal X-ray diffraction analysis. Raman and UV-vis-NIR spectroscopies further confirm the assignment of the cage isomers. Electrochemical gaps suggest that both Th@(9)-C and Th@(5)-C possess a stable closed-shell electronic structure. The computational results further confirm that Th@(9)-C and Th@(5)-C exhibit a unique four-electron charge transfer from the metal to the carbon cage and are among the most abundant isomers of Th@C.
与镧系元素类似物相比，锕系元素内嵌富勒烯已展现出显著不同的物理化学性质。在这项工作中，成功合成、分离出两种新型的Th@C异构体，并通过质谱、X射线单晶晶体学、紫外-可见-近红外光谱、拉曼光谱和循环伏安法对其进行了全面表征。通过单晶X射线衍射分析明确确定了这两种异构体的分子结构分别为Th@(9)-C和Th@(5)-C。拉曼光谱和紫外-可见-近红外光谱进一步证实了笼状异构体的归属。电化学能隙表明Th@(9)-C和Th@(5)-C均具有稳定的闭壳层电子结构。计算结果进一步证实，Th@(9)-C和Th@(5)-C表现出从金属到碳笼的独特四电子电荷转移，并且是Th@C中最丰富的异构体之一。
