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Synthesis of a distinct water dimer inside fullerene C70

Nature Chemistry volume 8, pages 435–441 (2016)Cite this article

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Abstract

The water dimer is an ideal chemical species with which to study hydrogen bonds. Owing to the equilibrium between the monomer and oligomer structure, however, selective generation and separation of a genuine water dimer has not yet been achieved. Here, we report a synthetic strategy that leads to the successful encapsulation of one or two water molecules inside fullerene C70. These endohedral C70 compounds offer the opportunity to study the intrinsic properties of a single water molecule without any hydrogen bonding, as well as an isolated water dimer with a single hydrogen bond between the two molecules. The unambiguously determined off-centre position of water in (H2O)2@C70 by X-ray diffraction provides insights into the formation of (H2O)2@C70. Subsequently, the 1H NMR spectroscopic measurements for (H2O)2@C70 confirmed the formation of a single hydrogen bond rapidly interchanging between the encapsulated water dimer. Our theoretical calculations revealed a peculiar cis-linear conformation of the dimer resulting from confinement effects inside C70.

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Figure 1: Structures of fullerene C60, C70 and their endohedral molecules.
Figure 2: Synthesis of open-cage C70 derivatives.
Figure 3: Synthesis of H2O@C70.
Figure 4: X-ray structure of the co-crystal of H2O@C70 and nickel(II) octaethylporphyrin with thermal ellipsoids set at the 50% level.
Figure 5: HPLC traces, APCI MS charts and 1H NMR spectra of a mixture of empty C70, H2O@C70 and (H2O)2@C70.
Figure 6: Computational studies of the water dimer encapsulated inside C70 and free dimer in the gas phase.

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Acknowledgements

Financial support was partially provided by the PRESTO programme on ‘Molecular Technology and Creation of New Functions’ from the JST, the JSPS KAKENHI (grant no. 23241032 and 15K13641) and Grant-in-Aids for Scientific Research on Innovative Areas ‘π-System Figuration: Control of Electron and Structural Dynamism for Innovative Functions’ and ‘Stimuli-responsive Chemical Species for the Creation of Functional Molecules’ from the MEXT, Japan. NMR measurements were supported by the Joint Usage/Research Center (JURC) at the ICR, Kyoto University. The authors thank T. Futagoishi, O. Tomita, H. Kunioku, R. Abe, Y. Kitazumi and K. Kano for support with X-ray and infrared measurements.

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Authors and Affiliations

  1. Institute for Chemical Research, Kyoto University, Uji, 611-0011, Kyoto, Japan

    Rui Zhang, Michihisa Murata, Tomoko Aharen, Atsushi Wakamiya, Takafumi Shimoaka, Takeshi Hasegawa & Yasujiro Murata

  2. JST, PRESTO, 4-1-8 Honcho, Kawaguchi, 332-0012, Saitama, Japan

    Yasujiro Murata

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Contributions

Y.M. conceived and designed the projects. R.Z. carried out most of the experimental works and theoretical calculations, and wrote the paper supported by M.M., T.A. and A.W. T.S. and T.H. performed the infrared measurements.

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Correspondence to Yasujiro Murata.

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Crystallographic data for compound H2O@C70. (CIF 61 kb)

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Structure factors file for compound H2O@C70. (FCF 637 kb)

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Zhang, R., Murata, M., Aharen, T. et al. Synthesis of a distinct water dimer inside fullerene C70. Nature Chem 8, 435–441 (2016). https://doi.org/10.1038/nchem.2464

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