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Up–down approach for expanding the chemical space of metal–organic frameworks

Nature Synthesis volume 3, pages 1518–1528 (2024)Cite this article

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Abstract

The vast structural diversity of metal–organic frameworks (MOFs) and the ability to tailor the structures makes the materials applicable for a broad range of uses. Traditional bottom-up and top-down design approaches have enabled a rapid increase in this structural diversity, yet the systematic screening for unknown synthesizable MOFs remains a challenge. Here we report a design strategy, the up–down approach, by merging the bottom-up and top-down approaches. This approach bridges the advantages of both methods, creating a synergistic strategy for discovering MOF structures. Targeting Zr-based MOFs, we search promising topology candidates and unveiled 26 future structural configurations by considering the possible orientations of Zr6 clusters. Through ribbon representation and sophisticated analysis of the ligand angles, we suggest structure models and synthesize Zr6-based MOFs with bct (1) and scu (1) configurations. The up–down approach will accelerate the discovery of previously unknown or inaccessible MOFs, providing exciting opportunities to expand the chemical space of MOFs.

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Fig. 1: Up–down approach for MOF discovery.
Fig. 2: Flowchart for screening possible topologies of Zr6-based MOFs.
Fig. 3: Ribbon representation to visualize molecular configurations and transformations of ligands.
Fig. 4: Ligand angle distribution for molecular configurations.
Fig. 5: Ligands for known and unknown Zr6-based MOFs.
Fig. 6: Discovery of new Zr6-based MOFs with bct (1) and scu (1) configurations.

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Data availability

The data supporting the findings of this study are available in this Article and its Supplementary Information. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers CCDC 2350674 (UMOF-10), 2235854 (UPF-100) and 2235855 (UPF-101). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

This work was supported by the National Research Foundation (NRF) of Korea (RS-2023-00279793, NRF-2020R1A2C3008226, NRF-2021M3I3A1084909, NRF-2021R1A6A6018767 and NRF-2016R1A5A1009405), the Carbon Neutral Institute Research Fund (1.220099.01) and the UBSI Research Fund (1.230069.01) of Ulsan National Institute of Science and Technology (UNIST). Jiy.K. and H.J.C. acknowledge the support from the NRF grants funded by the Korean Government (NRF-2018H1A2A1061391 (Global Ph.D. Fellowship Program) and NRF-2021R1A6A3A13043905). The authors acknowledge the Pohang Accelerator Laboratory (PAL) for 2D beamline use (2022-2nd-2D-034) and 6D beamline use (2024-1st-6D-A029). The authors thank Junghye Lee, H. Cho and Jinhyu Lee for their valuable discussions and efforts in attempting MOF synthesis.

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Author notes

  1. These authors contributed equally: Jiyeon Kim, Dongsik Nam, Hye Jin Cho.

Authors and Affiliations

  1. Department of Chemistry, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Jiyeon Kim, Dongsik Nam, Hye Jin Cho, Eunchan Cho, Dharmalingam Sivanesan, Changhyeon Cho & Wonyoung Choe

  2. Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology, Daejeon, Republic of Korea

    Jaewoong Lee & Jihan Kim

  3. Graduate School of Carbon Neutrality, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Wonyoung Choe

  4. Graduate School of Artificial Intelligence, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Wonyoung Choe

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Contributions

Conceptualization: W.C., Jiyeon Kim and D.N.; development of UDA methodology and analysis of ligand angles: Jiyeon Kim, D.N. and W.C.; investigation: Jiyeon Kim, D.N., E.C. and W.C.; synthesis and characterization of MOFs: Jiyeon Kim, D.N., H.J.C. and C.C.; synthesis of ligands: H.J.C. and D.S.; DFT calculations: J.L. and Jihan Kim; writing—original draft: Jiyeon Kim and D.N.; writing—review and editing: Jiyeon Kim, D.N., J.L., Jihan Kim and W.C; funding acquisition: W.C.

Corresponding author

Correspondence to Wonyoung Choe.

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Peer review information

Nature Synthesis thanks Christopher Wilmer, Stefan Wuttke and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary figures, discussion, tables and schemes.

Supplementary Data 1

ZIP file of the molecular configuration CIF files.

Supplementary Data 2

ZIP file of the model structure CIF files.

Supplementary Data 3

Crystallographic data for UMOF-10, CCDC 2350674.

Supplementary Data 4

Crystallographic data for UPF-100, CCDC 2235854.

Supplementary Data 5

Crystallographic data for UPF-101, CCDC 2235855.

Supplementary Video 1

Video about the formation process of UPF-101 from UPF-100.

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Kim, J., Nam, D., Cho, H.J. et al. Up–down approach for expanding the chemical space of metal–organic frameworks. Nat. Synth 3, 1518–1528 (2024). https://doi.org/10.1038/s44160-024-00638-x

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