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

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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Fig. 1: Chemical structure and in situ AFM image of PCP 1.
Fig. 2: Experimental set-up for in situ AFM imaging.
Fig. 3: Lattice-resolution image of the {001} facet of PCP 1 at the liquid–solid interface.
Fig. 4: Guest-induced lattice deformation tracked by in situ AFM imaging.
Fig. 5: Layer-by-layer delamination process captured in situ at the lattice scale.
Fig. 6: Plausible mechanism of <110> directional delamination.

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.

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Authors

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.

Corresponding authors

Correspondence to Nobuhiko Hosono or Susumu Kitagawa.

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Supplementary information

Supplementary Information

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

Crystallographic data

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

Crystallographic data

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

Crystallographic data

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

Crystallographic data

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

Crystallographic data

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

Crystallographic data

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

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Hosono, N., Terashima, A., Kusaka, S. et al. Highly responsive nature of porous coordination polymer surfaces imaged by in situ atomic force microscopy. Nature Chem 11, 109–116 (2019). https://doi.org/10.1038/s41557-018-0170-0

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