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Selective sorption of oxygen and nitric oxide by an electron-donating flexible porous coordination polymer

Nature Chemistry volume 2, pages 633637 (2010) | Download Citation

Abstract

Porous coordination polymers are materials formed from metal ions that are bridged together by organic linkers and that can combine two seemingly contradictory properties—crystallinity and flexibility. Porous coordination polymers can therefore create highly regular yet dynamic nanoporous domains that are particularly promising for sorption applications. Here, we describe the effective selective sorption of dioxygen and nitric oxide by a structurally and electronically dynamic porous coordination polymer built from zinc centres and tetracyanoquinodimethane (TCNQ) as a linker. In contrast to a variety of other gas molecules (C2H2, Ar, CO2, N2 and CO), O2 and NO are accommodated in its pores. This unprecedented preference arises from the concerted effect of the charge-transfer interaction between TCNQ and these guests, and the switchable gate opening and closing of the pores of the framework. This system provides further insight into the efficient recognition of small gas molecules.

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Acknowledgements

The authors thank S. Sakaki (Kyoto University) for his help in establishing the theoretical approach. XRPD experiments were performed at the BL02B2 in SPring-8 (proposal no. 2008B1263). This work was supported by an Exploratory Research for Advanced Technology (ERATO) project by Japan Science and Technology Agency (JST) ‘Kitagawa Integrated Pores Project’, and Riken Project in ‘Quantum Order Research Program’. Computation time was provided by the SuperComputer Laboratory, Institute for Chemical Research, Kyoto University.

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Affiliations

  1. Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8510, Japan

    • Satoru Shimomura
    • , Ko Yoneda
    • , Yuh Hijikata
    •  & Susumu Kitagawa
  2. RIKEN, SPring-8 Center, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148, Japan

    • Masakazu Higuchi
    • , Yoshiki Kubota
    • , Masaki Takata
    •  & Susumu Kitagawa
  3. ERATO Kitagawa Integrated Pores Project (Japan), Kyoto Research Park Building #3, Shimogyo-ku, Kyoto 600-8815, Japan

    • Ryotaro Matsuda
    •  & Susumu Kitagawa
  4. Institute for Integrated Cell-Material Sciences, Kyoto University 69 Konoe-cho, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan

    • Ryotaro Matsuda
    •  & Susumu Kitagawa
  5. Department of Physical Science, Graduate School of Science, Osaka Prefecture University, Osaka 599-8531, Japan

    • Yoshiki Kubota
  6. Division of Materials Physics, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan

    • Yoshimi Mita
  7. Japan Synchrotron Radiation Research Institute, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan

    • Jungeun Kim
    •  & Masaki Takata

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Contributions

S.S. and S.K. designed and conceived the experiments with support from K.Y. and Y.H. S.S., M.H. and Y.M. measured the Raman spectra. S.S., M.H., R.M., Y.K., J.K. and M.T. performed XRPD measurements and analysis. S.S., R.M. and S.K. contributed to writing the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Susumu Kitagawa.

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    Crystallographic information for compound 1 with tetrafluorobenzene guests

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DOI

https://doi.org/10.1038/nchem.684

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