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Bottom-up realization of a porous metal–organic nanotubular assembly

Nature Materials volume 10, pages 291–295 (2011)Cite this article

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Abstract

Nanotubes are generally prepared from their constituent elements at high temperatures, and thus it is difficult to control their size, shape and electronic states1,2,3,4,5,6,7,8,9,10. One useful approach for synthesizing well-defined nanostructures involves the use of building blocks such as metal ions and organic molecules11,12,13,14. Here, we show the successful creation of an assembly of infinite square prism-shaped metal–organic nanotubes obtained from the simple polymerization of a square-shaped metal–organic frame. The constituent nanotube has a one-dimensional (1D) channel with a window size of 5.9×5.9 Å2, and can adsorb water (H2O) and alcohol vapours, whereas N2 and CO2 do not adhere. It consists of four 1D covalent chains that constitute a unique electronic structure of ‘charge-density wave (CDW) quartets’ on crystallization. Moreover, exchanging structural components and guest molecules enables us to control its semiconductive bandgap. These findings demonstrate the possibility of bottom-up construction of new porous nanotubes, where their degrees of freedom in both pore space and framework can be used.

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Figure 1: Rational design for the metal–organic nanotube.
Figure 2: Experimental confirmation of the porosity.
Figure 3: Clarification of the electronic structure of 1.
Figure 4: Theoretical approach for the electronic ground-state of 1.

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Acknowledgements

Synchrotron XRPD and diffuse X-ray scattering measurements were supported by High Energy Accelerator Research Organization (KEK), Japan (Proposal no. 2008G068). Synchrotron XAFS measurements were supported by Japan Synchrotron Radiation Research Institute (JASRI) (Proposal no. 2010B1975). This work was partly supported by Research Fellowships for Young Scientists (No. 1910614) from the JSPS. H.O. is grateful for support by a Grant-in-Aid for Scientific Research (No. 20110005) by the Ministry of Education, Culture, Sports, Science and Technology of Japan.

Author information

Author notes

  1. Jun Ohara

    Present address: Present address: Department of Physics, Graduate School of Science, Tohoku University, Aza-Aoba, Aramaki, Aoba-ku, Sendai, Miyagi 980-8578, Japan,

Authors and Affiliations

  1. Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto 606-8502, Japan

    Kazuya Otsubo & Hiroshi Kitagawa

  2. Department of Chemistry, Faculty of Science, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan

    Kazuya Otsubo & Hiroshi Kitagawa

  3. Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), 5 Sanban-cho, Chiyoda-ku, Tokyo 102-0075, Japan

    Kazuya Otsubo, Hiroshi Okamoto & Hiroshi Kitagawa

  4. Division of Materials Physics, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama-cho, Toyonaka, Osaka 560-8531, Japan

    Yusuke Wakabayashi

  5. Division of Physics, Faculty of Science, Hokkaido University, Kita-10, Nishi-8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan

    Jun Ohara & Shoji Yamamoto

  6. Department of Advanced Materials Science, Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561, Japan

    Hiroyuki Matsuzaki & Hiroshi Okamoto

  7. Japan Synchrotron Radiation Research Institute (JASRI), SPring-8, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo, 679-5198, Japan

    Kiyofumi Nitta & Tomoya Uruga

  8. Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan

    Hiroshi Kitagawa

  9. INAMORI Frontier Research Center, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-3095, Japan

    Hiroshi Kitagawa

Authors
  1. Kazuya Otsubo
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Contributions

H.K. and K.O. designed and directed this study, and analysed the experimental results. K.O. contributed to all of the experimental work. Y.W. carried out synchrotron diffuse X-ray scattering measurements. J.O. and S.Y. conducted theoretical calculations. H.M. and H.O. contributed to single-crystal reflectance spectroscopy. K.N. and T.U. carried out synchrotron XAFS measurements. K.O., Y.W., J.O., S.Y. and H.K. co-wrote the manuscript. All authors commented on the paper.

Corresponding authors

Correspondence to Kazuya Otsubo or Hiroshi Kitagawa.

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Otsubo, K., Wakabayashi, Y., Ohara, J. et al. Bottom-up realization of a porous metal–organic nanotubular assembly. Nature Mater 10, 291–295 (2011). https://doi.org/10.1038/nmat2963

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