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Endohedral Lithium-containing Fullerenes pp 51–88Cite as

Chemical Modification of Li+@C60

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Abstract

The synthesis of lithium-ion-containing [6,6]-phenyl-C61-butyric acid methyl ester (Li+@PCBM) was first demonstrated through the organic functionalization of Li+@C60. The [5,6]- and [6,6]-isomers of [Li+@PCBM]PF6 − were successfully prepared, and the structure of [6,6]-[Li+@PCBM]PF6 − was elucidated by X-ray crystallography. The Diels–Alder reaction of Li+@C60 was first investigated using cyclopentadiene as a diene. This reaction was fast, with an equilibrium constant of more than 1000-fold that for the reaction with the C60. The Diels–Alder reaction of [Li+@C60]PF6 − with 1,3-cyclohexadiene was also experimentally and computationally investigated to precisely determine the kinetic parameters. Li+@C60 reacted 2400-fold faster, compared with the empty C60. Li+-containing fullerenol was synthesized through cyclosulfation followed by hydrolysis. The reaction proceeded with good regioselectively, and the product was highly soluble, even in polar solvents. Iridium and platinum complexes of Li+@C60 were synthesized, and an electrostatic attractive interaction between inner Li+ and outer transition metals was demonstrated. A supramolecular complex of [10]cycloparaphenylene and Li+@C60 was also synthesized. Charge delocalization of the inner cationic charge on outer [10]cycloparaphenylene through C60 π-conjugated system was suggested.

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Authors and Affiliations

  1. University of Science and Technology of China, Hefei, China

    Yutaka Matsuo

  2. The University of Tokyo, Tokyo, Japan

    Hiroshi Okada

  3. Northeast Normal University, Changchun, China

    Hiroshi Ueno

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  1. Yutaka Matsuo
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  2. Hiroshi Okada
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  3. Hiroshi Ueno
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Correspondence to Yutaka Matsuo .

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Matsuo, Y., Okada, H., Ueno, H. (2017). Chemical Modification of Li+@C60 . In: Endohedral Lithium-containing Fullerenes. Springer, Singapore. https://doi.org/10.1007/978-981-10-5004-6_5

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