•  
  •  
 
Nano Research

Article Title

Highly delocalized endohedral metal in Gd@C2v(9)-C82 metallofullerenes co-crystallized with α-S8

Authors

Cheng Li, CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China University of Chinese Academy of Sciences, Beijing 100049, China
Xuejiao J. Gao, College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China
Huanli Yao, CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China University of Chinese Academy of Sciences, Beijing 100049, China
Huan Huang, CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China University of Chinese Academy of Sciences, Beijing 100049, China
Rongli Cui, CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China University of Chinese Academy of Sciences, Beijing 100049, China
Xihong Guo, CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China University of Chinese Academy of Sciences, Beijing 100049, China
Lele Zhang, CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Bing Liu, CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China University of Chinese Academy of Sciences, Beijing 100049, China
Binggang Xu, CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Weiqun Shi, CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China University of Chinese Academy of Sciences, Beijing 100049, China
Jinquan Dong, CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Lai Feng, College of Physics, Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215006, China
Xingfa Gao, College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China
Baoyun Sun, CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China University of Chinese Academy of Sciences, Beijing 100049, China

Keywords

metallofullerenes, sulfur, structure elucidation, delocalization, density functional theory (DFT) calculations

Abstract

ABSTRACT A new Gd@C2v(9)-C82·2.5(S8)·0.5(CS2) co-crystal was prepared for the first time and characterized by single-crystal X-ray diffraction (XRD). The analysis clearly showed that, even though the C2v(9)-C82 cage is fully ordered, the endohedral Gd atoms are highly disordered. This result indicates the presence of highly delocalized endohedral Gd atoms, which has never been reported before. Density functional theory (DFT) calculations were used to rationalize the XRD results. The calculations reveal the presence of two local energy minima, a and b, with the latter existing as four conformers b1–b4. Whereas the energy difference between the two minima is calculated only ~ 10 kcal/mol, their interconversion is almost impossible due to a high energy barrier, of up to 35.98 kcal/mol. This suggests the existence of multiple low-energy positions for the endohedral Gd atom. In addition, a remarkable electron transfer from the C2v(9)-C82 cage to the S8 moieties was demonstrated, which might result in a modified endohedral environment and further contribute to the occurrence of delocalized endohedral Gd atoms.

Graphical Abstract

Publisher

Tsinghua University Press

Share

COinS