Abstract
If the physical properties of C60 fullerene molecules can be controlled in C60 products already in use in various applications, the potential for industrial development will be significant. Encapsulation of a metal atom in the C60 fullerene molecule is a promising way to control its physical properties. However, the isolation of C60-based metallofullerenes has been difficult due to their insolubility. Here, we report the complete isolation and determination of the molecular and crystal structure of polar cationic Li@C60 metallofullerene. The physical and chemical properties of Li@C60 cation are compared with those of pristine C60. It is found that the lithium cation is located at off-centre positions in the C60–Ih cage interior and that the [Li+@C60] salt has a unique two-dimensional structure. The present method of purification and crystallization of C60-based metallofullerenes provides a new C60 fullerene material that contains a metal atom.
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Acknowledgements
This research was partially supported by a Ministry of Education, Culture, Sports, Science and Technology Grant-in-Aid for Scientific Research (A) (20244059) and Scientific Research on Priority Areas (19051015). This work was also supported by the Ministry of Economy, Trade and Industry, the Miyagi Prefectural Government, Sendai city, and the Japan Science and Technology Agency. We are grateful to R. Hatakeyama for help in the construction and operation of the plasma reactor, Y. Takabayashi for fruitful discussions, and T. Kawaguchi and H. Ikuta for the resistivity measurement. We also acknowledge the Technical Division, School of Engineering, and Analytical Center for Giant Molecules, Graduate School of Science of Tohoku University for developing the metallofullerene synthesis apparatus and for spectroscopic and analytical measurements. The synthesis and crystallization of [Li@C60](SbCl6) were carried out in Sendai, and the XRD and analyses were performed in SPring-8 and Nagoya, respectively. The SR experiments were performed at SPring-8 with approval of the Japan Synchrotron Radiation Research Institute (JASRI).
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H. Sawa, H. Shinohara, H.T. and Y.K. were responsible for designing and coordinating this study. S.A., E.N. and H. Sawa interpreted and discussed the results and carried out single-crystal XRD measurements and structural analysis. K.K., K.Y. and Y.K. carried out the synthesis. H.O., T.S., T.K. and S.I. carried out purification, crystallization, LDI–TOF mass and NMR measurements. H. Shinohara, Y.M., R.K., Y.O., K.O. and S.O. were involved in experiments and discussions. M.T. and K.S. carried out the SR-XRD measurements. All authors commented on the paper, which was written by H. Sawa and H.T.
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Aoyagi, S., Nishibori, E., Sawa, H. et al. A layered ionic crystal of polar Li@C60 superatoms. Nature Chem 2, 678–683 (2010). https://doi.org/10.1038/nchem.698
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DOI: https://doi.org/10.1038/nchem.698
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