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

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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.

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Acknowledgements

This work was financially supported by the National Basic Research Program of China (No. 2016YFA0203200) and the National Natural Science Foundation of China (Nos. 51372158, 21402202, 11505191 and U1632113).

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Author notes

  1. Cheng Li and Xuejiao J. Gao contributed equally to this work.

Authors and Affiliations

  1. CAS Key Lab for Biomedical Effects of Nanomaterials & Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China

    Cheng Li, Huanli Yao, Huan Huang, Rongli Cui, Xihong Guo, Lele Zhang, Bing Liu, Binggang Xu, Weiqun Shi, Jinquan Dong & Baoyun Sun

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Cheng Li, Huanli Yao, Huan Huang, Rongli Cui, Xihong Guo, Bing Liu, Weiqun Shi & Baoyun Sun

  3. College of Physics, Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou, 215006, China

    Lai Feng

  4. College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, 330022, China

    Xuejiao J. Gao & Xingfa Gao

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  1. Cheng Li
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Correspondence to Lai Feng, Xingfa Gao or Baoyun Sun.

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Li, C., Gao, X.J., Yao, H. et al. Highly delocalized endohedral metal in Gd@C2v(9)-C82 metallofullerenes co-crystallized with α-S8. Nano Res. 11, 2277–2284 (2018). https://doi.org/10.1007/s12274-017-1849-z

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