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Highly responsive nature of porous coordination polymer surfaces imaged by in situ atomic force microscopy

Nature Chemistry (2018) | Download Citation

Abstract

The ability of porous coordination polymers to undergo reversible structural transformations in response to the presence of guest molecules has been intensively investigated for applications such as molecular separation, storage, sensing and signalling processes. Here we report on the direct observation of the highly guest-responsive nature of the surface of a single-crystalline porous coordination polymer, which consists of paddlewheel zinc clusters and two types of ligand, by in situ liquid-phase atomic force microscopy. Observations were carried out in solution at constant temperature (28 °C) by high-speed atomic force microscopy with lattice resolution. A sharp and reversible response to the presence or absence of biphenyl guest molecules was observed, under conditions that can scarcely induce the transformation of the bulk crystal. Additionally, by modulating the surface coordination equilibrium, layer-by-layer delamination events were captured in real time at every ~13 s per frame.

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Data availability

Crystallographic data for PCP 1 at different temperatures have been deposited at the Cambridge Crystallographic Data Centre, under deposition nos. CCDC 1864180 (10 °C), 1864181 (20 °C) and 1864182 (28 °C). Copies of the data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif. All other data supporting the findings of this study are available within the Article and its Supplementary Information, or from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by a KAKENHI Grant-in-Aid for Specially Promoted Research (JP25000007) and Scientific Research (S) (JP18H05262) from the Japan Society of the Promotion of Science (JSPS). N.H. acknowledges JSPS for KAKENHI Grants-in-Aid for Young Scientists (B) ( JP16K17959) and Scientific Research (B) (JP18H02072), and the Regional Innovation Strategy Support Program (Next-generation Energy System Creation Strategy for Kyoto) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. S.Ki. acknowledges the ACCEL programme (JPMJAC1302) of JST for financial support. This work was also supported by a Grant for Basic Science Research Projects from The Sumitomo Foundation. H. Sato (The University of Tokyo) and N. Shimanaka (Kyoto University) are thanked for useful discussions about the experiments and technical single-crystal X-ray analysis support, respectively.

Author information

Author notes

    • Nobuhiko Hosono

    Present address: Department of Advanced Materials Science, Graduate School of Frontier Sciences, The University of Tokyo, Kashiwanoha, Kashiwa, Chiba, Japan

    • Shinpei Kusaka
    •  & Ryotaro Matsuda

    Present address: Department of Materials Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Japan

Affiliations

  1. Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University Institute for Advanced Study (KUIAS), Kyoto University, Kyoto, Japan

    • Nobuhiko Hosono
    • , Aya Terashima
    • , Shinpei Kusaka
    • , Ryotaro Matsuda
    •  & Susumu Kitagawa

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Contributions

N.H. and S.Ki. conceived this study. N.H. and A.T. designed the experiments. N.H. and A.T. performed the material synthesis, AFM imaging and data analysis. N.H. and S.Ki. supervised the research. All authors interpreted the results, and N.H., S.Ku. R.M. and S.Ki co-wrote the manuscript with input from all the authors.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Nobuhiko Hosono or Susumu Kitagawa.

Supplementary information

  1. Supplementary Information

    Supplementary Materials; Supplementary Scheme 1 and Figures 1–19; X-ray diffraction analysis; Supplementary Table 1; Supplementary References 1–7.

  2. Crystallographic data

    Structure-factor file for PCP 1 at 10 °C; CCDC reference: 1864180

  3. Crystallographic data

    Structure-factor file for compound PCP 1 at 10 °C; CCDC reference: 1864180

  4. Crystallographic data

    Structure-factor file for compound PCP 1 at 20 °C; CCDC reference: 1864181

  5. Crystallographic data

    Structure-factor file for compound PCP 1 at 20 °C; CCDC reference: 1864181

  6. Crystallographic data

    Structure-factor file for compound PCP 1 at 28 °C; CCDC reference: 1864182

  7. Crystallographic data

    Structure-factor file for compound PCP 1 at 28 °C; CCDC reference: 1864182

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DOI

https://doi.org/10.1038/s41557-018-0170-0