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A layered ionic crystal of polar Li@C60 superatoms

Nature Chemistry volume 2, pages 678–683 (2010)Cite this article

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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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Figure 1: LDI–TOF mass spectra and NMR spectra of [Li@C60](SbCl6).
Figure 2: Cyclic (CVs) and differential pulse voltammograms (DPVs) of [Li@C60](SbCl6), C60 and (Et4N)(SbCl6) in the region of their reduction (0 to −3.0 V versus ferrocene (Fc)/ferrocenium (Fc+)).
Figure 3: MEM charge density distributions of a Li@C60 cation in [Li@C60](SbCl6) crystal.
Figure 4: Structure of [Li+@C60].
Figure 5: Layered crystal structure of [Li@C60](SbCl6).

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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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Authors and Affiliations

  1. Department of Applied Physics, Nagoya University, Nagoya, 464-8603, Japan

    Shinobu Aoyagi, Eiji Nishibori & Hiroshi Sawa

  2. SPring-8/JASRI, Kouto, Sayo, Hyogo, 679-5198, Japan

    Kunihisa Sugimoto & Masaki Takata

  3. RIKEN SPring-8 Center, Kouto, Sayo, Hyogo, 679-5148, Japan

    Kunihisa Sugimoto & Masaki Takata

  4. Department of Chemistry and Institute for Advanced Research, Nagoya University, Nagoya, 464-8602, Japan

    Yasumitsu Miyata, Ryo Kitaura & Hisanori Shinohara

  5. Ideal Star Inc., 6-6-3 Minamiyoshinari, Aoba-ku, Sendai, 989-3204, Japan

    Hiroshi Okada, Takeshi Sakai, Yoshihiro Ono, Kazuhiko Kawachi, Kuniyoshi Yokoo, Shoichi Ono, Kenji Omote & Yasuhiko Kasama

  6. Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, 980-8578, Japan

    Shinsuke Ishikawa, Takashi Komuro & Hiromi Tobita

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Contributions

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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Correspondence to Hiroshi Sawa or Hiromi Tobita.

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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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