Unique Four-Electron Metal-to-Cage Charge Transfer of Th to a C82Fullerene Cage: Complete Structural Characterization of Th@C3v(8)-C82.
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)-C82is 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)-C82displays a strong vibrationally coupled photoluminescence signal in the visible region, an extremely rare feature for both fullerenes and thorium compounds.
Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou, Jiangsu 215123, P.R. China.
Yaofeng
Y
Wang
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili , c/Marcel·lí Domingo 1, 43007 Tarragona, Spain.
Roser
R
Morales-Martínez
Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou, Jiangsu 215123, P.R. China.
Xingxing
X
Zhang
Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou, Jiangsu 215123, P.R. China.
Wei
W
Yang
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.
Yaxing
Y
Wang
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili , c/Marcel·lí Domingo 1, 43007 Tarragona, Spain.
Antonio
A
Rodríguez-Fortea
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili , c/Marcel·lí Domingo 1, 43007 Tarragona, Spain.
Josep M
http://orcid.org/0000-0002-4533-0623
JM
Poblet
Soochow Institute for Energy and Materials Innovations (SIEMIS), College of Physics, Optoelectronics and Energy, Soochow University , Suzhou, Jiangsu 215006, China.
Lai
L
Feng
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.
Shuao
http://orcid.org/0000-0002-1526-1102
S
Wang
Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou, Jiangsu 215123, P.R. China.
Ning
http://orcid.org/0000-0002-9405-6229
N
Chen