Unique Four-Electron Metal-to-Cage Charge Transfer of Th to a C82 Fullerene Cage: Complete Structural Characterization of Th@C3v(8)-C82
Yaofeng Wang†⊥, Roser Morales-Martínez‡⊥, Xingxing Zhang†, Wei Yang†, Yaxing Wang∥, Antonio Rodríguez-Fortea*‡, Josep M. Poblet‡, Lai Feng*§（冯莱）, Shuao Wang*∥（王殳凹）, and Ning Chen*†（谌宁）
† 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
§ Soochow Institute for Energy and Materials Innovations (SIEMIS), College of Physics, Optoelectronics and Energy, Soochow University, Suzhou, Jiangsu 215006, China
∥ School of Radiological and Interdisciplinary Sciences & Collaborative Innovation Center of Radiation Medicine of Jiangsu, Higher Education Institutions, Soochow University, Suzhou, Jiangsu 215123, P.R. China
J. Am. Chem. Soc., 2017, 139 (14), pp 5110–5116
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@C82, 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@C3v(8)-C82. Combined experimental and theoretical studies reveal that Th@C3v(8)-C82 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@C3v(8)-C82 displays a strong vibrationally coupled photoluminescence signal in the visible region, an extremely rare feature for both fullerenes and thorium compounds.
链接：http://pubs.acs.org/doi/abs/10.1021/jacs.6b13383