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Rapid desolvation-triggered domino lattice rearrangement in a metal–organic framework

Nature Chemistry volume 12, pages 90–97 (2020)Cite this article

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A Publisher Correction to this article was published on 10 December 2019

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Abstract

Topological transitions between considerably different phases typically require harsh conditions to collectively break chemical bonds and overcome the stress caused to the original structure by altering its correlated bond environment. In this work we present a case system that can achieve rapid rearrangement of the whole lattice of a metal–organic framework through a domino alteration of the bond connectivity under mild conditions. The system transforms from a disordered metal–organic framework with low porosity to a highly porous and crystalline isomer within 40 s following activation (solvent exchange and desolvation), resulting in a substantial increase in surface area from 725 to 2,749 m2 g–1. Spectroscopic measurements show that this counter-intuitive lattice rearrangement involves a metastable intermediate that results from solvent removal on coordinatively unsaturated metal sites. This disordered–crystalline switch between two topological distinct metal–organic frameworks is shown to be reversible over four cycles through activation and reimmersion in polar solvents.

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Fig. 1: The structural illustration of the building blocks in AlTz-53 and AlTz-68.
Fig. 2: The lattice rearrangement in an Al-MOF.
Fig. 3: Characterization of the reversible transformation between AlTz-53 and AlTz-68.
Fig. 4: The spectroscopic characterization of AlTz-53-DMF, AlTz-53-DEF and AlTz-68.
Fig. 5: The proposed mechanism of lattice rearrangement from AlTz-53 to AlTz-68.
Fig. 6: A reversible cascade lattice rearrangement via carboxylate linker migration following resolvation and desolvation.

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Data availability

All relevant data that support the findings of this study are available from the corresponding authors on request. The synthetic procedures, crystallographic, spectroscopic, computational and enzyme catalysis data are provided in the Supplementary Information. The unit-cell parameters and atomic positions were obtained by Rietveld refinement of the PXRD data, using the AlTz-53-DMF, AlTz-53-DEF and AlTz-68 crystal structural models reported in the Article. The X-ray crystallographic data for structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition nos. 1892351 (AlTz-53-DEF), 1892352 (AlTz-53-DMF) and 1892353 (AlTz-68). The data can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk/data_request/cif.

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Acknowledgements

We dedicate this paper to the memory of H.-Y. Huang (Department of Chemistry, Chung Yuan Christian University) for her enthusiasm for—and encouragement of—this work. The gas adsorption–desorption studies and enzyme immobilization of this research were supported by the Ministry of Science and Technology, Taiwan (under MOST-106-2113-M-033-001) and Chung Yuan Christian University. Thermogravimetric analysis–mass spectrometry, transmission electron microscopy, and PXRD characterization and analysis were funded by the Robert A. Welch Foundation through a Welch Endowed Chair to H.-C.Z. (A-0030). Solid-state NMR and scanning electron microscopy were supported by the Ministry of Science and Technology, Taiwan (under MOST-106-2113-M-007-023-MY2) and the National Tsing Hua University. The material syntheses were funded by the Ministry of Science and Technology, Taiwan (under MOST-103-2113-M-001-005-MY3) and Academia Sinica. The spectroscopic characterization and analysis (infrared) work were supported by the US Department of Energy (under award no. DE-FG02-08ER46491, and finished under award no. DE-SC0019902). The authors acknowledge the support with a 01C2 beam line from the National Synchrotron Radiation Research Center (NSRRC), Taiwan. The PDF structural analyses were supported by the US Department of Energy, Office of Science and Office of Basic Energy Sciences (DOE‐BES) (under contract no. DE-SC0017864), the Knut and Alice Wallenberg Foundation (KAW) (3DEM-NATUR project no. 2012.0112) and the Swedish Research Council (VR, 2017–04321). S.J.L.B. and S.T. were supported for PDF analysis by the NSF MRSEC programme through Columbia University in the Center for Precision Assembly of Superstratic and Superatomic Solids (DMR-1420634). Use of the National Synchrotron Light Source II, Brookhaven National Laboratory, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (under contract no. DE-SC0012704). The authors also acknowledge the valuable assistance and discussion from H. Deng and J. Li.

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Author notes

  1. These authors contributed equally: Sheng-Han Lo, Liang Feng.

Authors and Affiliations

  1. Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan

    Sheng-Han Lo, Bing-Han Li & Sue-Lein Wang

  2. Institute of Chemistry, Academia Sinica, Taipei, Taiwan

    Sheng-Han Lo, Tzuoo-Tsair Luo & Kuang-Lieh Lu

  3. Department of Chemistry, Texas A&M University, College Station, TX, USA

    Liang Feng, Shuai Yuan, Kun-Yu Wang, Gregory S. Day & Hong-Cai Zhou

  4. Department of Materials Science and Engineering, University of Texas at Dallas, Richardson, TX, USA

    Kui Tan & Yves J. Chabal

  5. Berzelii Centre EXSELENT on Porous Materials and Inorganic and Structural Chemistry, Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, Sweden

    Zhehao Huang & Xiaodong Zou

  6. College of Science, Chung Yuan Christian University, Taoyuan City, Taiwan

    Wan-Ling Liu

  7. Department of Applied Physics and Applied Mathematics, Columbia University, New York, NY, USA

    Songsheng Tao & Simon J. L. Billinge

  8. Department of Physics, Chung Yuan Christian University, Taoyuan City, Taiwan

    Chun-Chuen Yang

  9. Department of Chemistry, Chung Yuan Christian University, Taoyuan City, Taiwan

    Chia-Her Lin & Sue-Lein Wang

  10. R&D Center for Membrane Technology, Chung Yuan Christian University, Taoyuan City, Taiwan

    Chia-Her Lin

  11. Department of Chemistry, National Taiwan Normal University, Taipei, Taiwan

    Chia-Her Lin

  12. Condensed Matter Physics and Materials Science Department, Brookhaven National Laboratory, Upton, NY, USA

    Simon J. L. Billinge

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Contributions

C.-H.L., S.-L.W., Y.J.C and H.-C.Z. conceived the research idea and designed the experiments. Experiments and data analysis were performed by S.-H.L., L.F., S.Y., C.-C.Y. and W.-L.L. Structure characterization was performed by K.T., Z. H., B.-H.L., G.S.D., S.T., S.J.L.B. and Y.J.C. Density functional theory calculations were performed by K.-Y.W. The manuscript was drafted by L.F., K.T., Y.J.C, T.-T.L., S.-H.L., K.-L.L., Z.H., X.Z. and H.-C.Z. All authors have approved the manuscript.

Corresponding authors

Correspondence to Chia-Her Lin, Sue-Lein Wang, Kuang-Lieh Lu, Yves J. Chabal or Hong-Cai Zhou.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

Synthetic procedures, crystallographic, spectroscopic, computational and enzyme catalysis data; Supplementary Figs. 1–47 and Refs. 1–25.

Supplementary Movie 1

Illustration of desolvation-triggered domino-like lattice rearrangement of Al-MOFs.

Crystallographic data

CIF for AlTz-53-DEF; CCDC number: 1892351.

Crystallographic data

CIF for AlTz-53-DMF; CCDC number: 1892352.

Crystallographic data

CIF for AlTz-68; CCDC number: 1892353.

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Lo, SH., Feng, L., Tan, K. et al. Rapid desolvation-triggered domino lattice rearrangement in a metal–organic framework. Nat. Chem. 12, 90–97 (2020). https://doi.org/10.1038/s41557-019-0364-0

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