Wang Yaofeng, Morales-Martínez Roser, Zhang Xingxing, Yang Wei, Wang Yaxing, Rodríguez-Fortea Antonio, Poblet Josep M, Feng Lai, Wang Shuao, Chen Ning
Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou, Jiangsu 215123, P.R. China.
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili , c/Marcel·lí Domingo 1, 43007 Tarragona, Spain.
J Am Chem Soc. 2017 Apr 12;139(14):5110-5116. doi: 10.1021/jacs.6b13383. Epub 2017 Mar 31.
Endohedral metallofullerenes (EMFs) containing lanthanides have been intensively studied in recent years. By contrast, actinide endohedral fullerenes remain largely unexplored. Herein, for the first time, we report the single crystal structure and full characterization of an actinide endohedral fullerene, Th@C, which exhibits remarkably different electronic and spectroscopic properties compared to those of lanthanide EMFs. Single crystal X-ray crystallography unambiguously established the molecular structure as Th@C(8)-C. Combined experimental and theoretical studies reveal that Th@C(8)-C is the first example of an isolated monometallofullerene with four electrons transferred from the metal to the cage, with a surprisingly large electrochemical band gap of 1.51 eV. Moreover, Th@C(8)-C displays a strong vibrationally coupled photoluminescence signal in the visible region, an extremely rare feature for both fullerenes and thorium compounds.
近年来，含镧系元素的内嵌金属富勒烯（EMFs）受到了广泛研究。相比之下，锕系内嵌富勒烯在很大程度上仍未被探索。在此，我们首次报道了一种锕系内嵌富勒烯Th@C的单晶结构及全面表征，它展现出与镧系EMFs显著不同的电子和光谱性质。单晶X射线晶体学明确确定其分子结构为Th@C(8)-C。结合实验和理论研究表明，Th@C(8)-C是首例从金属向笼转移四个电子的孤立单金属富勒烯，其电化学带隙高达1.51 eV，令人惊讶。此外，Th@C(8)-C在可见光区域显示出强烈的振动耦合光致发光信号，这对于富勒烯和钍化合物来说都是极为罕见的特征。
