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

Nature Chemistry volume 2, pages 633–637 (2010)Cite this article

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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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Figure 1: Details of the crystal structure of 1 (open form).
Figure 2: Guest-accommodating structures of 1 (open form).
Figure 3: Adsorption isotherms of several gas molecules.
Figure 4: Structural transformation of 1 accompanying guest sorption.
Figure 5: Infrared spectra of each state of 1.
Figure 6: Raman spectroscopy of 1 under a controlled atmosphere.

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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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Authors and Affiliations

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

    Satoru Shimomura, Ko Yoneda, Yuh Hijikata & Susumu Kitagawa

  2. RIKEN, SPring-8 Center, 1-1-1, Kouto, Sayo-cho, Sayo-gun, 679-5148, Hyogo, Japan

    Masakazu Higuchi, Yoshiki Kubota, Masaki Takata & Susumu Kitagawa

  3. ERATO Kitagawa Integrated Pores Project (Japan), Kyoto Research Park Building #3, Shimogyo-ku, 600-8815, Kyoto, Japan

    Ryotaro Matsuda & Susumu Kitagawa

  4. Institute for Integrated Cell-Material Sciences, Kyoto University 69 Konoe-cho, Yoshida, Sakyo-ku, 606-8501, Kyoto, 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, 560-8531, Osaka, Japan

    Yoshimi Mita

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

    Jungeun Kim & Masaki Takata

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  1. Satoru Shimomura
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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.

Corresponding author

Correspondence to Susumu Kitagawa.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 1305 kb)

Supplementary information

Crystallographic information for compound 1 with tetrafluorobenzene guests (CIF 22 kb)

Supplementary information

Crystallographic information for compound 1 with anisole guests (CIF 23 kb)

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Crystallographic information for compound 1 with benzonitrile guests (CIF 23 kb)

Supplementary information

Crystallographic information for compound 1 with p-xylene guests guests (CIF 28 kb)

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Shimomura, S., Higuchi, M., Matsuda, R. et al. Selective sorption of oxygen and nitric oxide by an electron-donating flexible porous coordination polymer. Nature Chem 2, 633–637 (2010). https://doi.org/10.1038/nchem.684

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