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Covalent organic frameworks as infinite building units for metal–organic frameworks with compartmentalized pores

Nature Chemistry (2025)Cite this article

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Abstract

Metal–organic frameworks typically rely on discrete molecules as building units, and creating frameworks featuring continuous organic or inorganic subnet moieties, such as chains and layers, is challenging. While all-inorganic subnets have been used as units with infinite connectivity, the intrinsic disorder in organic chains and layers hinders their role as well-defined building blocks for reticular materials. Here we report the one-pot synthesis of a series of Zr6O8-based or Hf6O8-based metal–organic frameworks that feature boroxine-based one-dimensional and two-dimensional covalent organic frameworks—chains with diverse conformations and layers with specific topology, respectively—as the organic components. The spatial compatibility between the constituents locks the infinite organic units into patterned arrangements and thus generates metal–organic frameworks with distinct structural entities and pore environments in separate sections along specific directions. The coexistence of extended covalent organic frameworks and discrete inorganic units, side by side and yet independent of each other, leads to high structural compartmentalization in space.

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Fig. 1: Strategies to construct infinite organic linkers and the resulting MOFs.
Fig. 2: 0D, 1D and 2D organic linkers in MOF-401‒MOF-406.
Fig. 3: Structures of MOF-401‒MOF-406 based on the designed 0D, 1D and 2D organic linkers and the Zr6O8-based SBUs.
Fig. 4: The spatial compatibility between the infinite linkers and the SBUs.
Fig. 5: Adsorption studies of the MOFs.

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Data availability

All data that support the findings of this study are available in the paper and its Supplementary Information. X-ray crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers 2416824 (for MOF-401), 2416825 (for MOF-402), 2416826 (for MOF-403), 2416827 (for MOF-404), 2416828 (for MOF-404-oF), 2416829 (for MOF-404-mF), 2416830 (for MOF-405), 2416831 (for MOF-406F), 2457479 (for MOF-401(Hf)), 2457480 (for MOF-403(Hf)), 2457481 (for MOF-404(Hf)) and 2457482 (for MOF-405(Hf)). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (grants 2018YFA0209401 and 2021YFA1500400), the National Natural Science Foundation of China (grants 21922103, 21961132003, 22088101, 22331009 and U22A20401) and the Science and Technology Commission of Shanghai Municipality (grant 2024ZDSYS02). We thank L. Hou, Z. Jiang and Y. Rao for their assistance with the structure refinement and illustration.

Author information

Author notes

  1. These authors contributed equally: Bo Liu, Yichen Wu.

Authors and Affiliations

  1. College of Chemistry & Pharmacy, Northwest A&F University, Yangling, China

    Bo Liu & Linxia Wang

  2. Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry, University of Science and Technology of China, Hefei, China

    Bo Liu & Hai-Long Jiang

  3. Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China

    Yichen Wu & Qiaowei Li

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Contributions

B.L., H.-L.J. and Q.L. conceived the project. H.-L.J. and Q.L. supervised the project. B.L. designed and performed the syntheses. B.L. and Y.W. performed the structure characterizations and porosity studies. L.W. also performed the syntheses. B.L., Y.W., H.-L.J. and Q.L. wrote the paper. All authors contributed to the data analysis, discussion and revision of the paper.

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Correspondence to Hai-Long Jiang or Qiaowei Li.

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Nature Chemistry thanks Shuhei Furukawa and Fernando Uribe-Romo for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Structures of MOF-401‒403.

Single crystal structures of MOF-401 (a) and MOF-402 (c), each depicting one spn net, and the structure of MOF-403 (e). The corresponding linkers, 0D-L1 (b), 0D-L2 (d), and 0D-L3 (f), are highlighted with their cores colored pink. Blue polyhedra represent Zr. Grey, red, and pink spheres represent C/N, O, and B atoms, respectively.

Extended Data Fig. 2 Structures of MOF-404 and MOF-405.

Single crystal structures of MOF-404 (a) and MOF-405 (c), and their corresponding linkers 1D-L1 (b) and 1D-L2 (d). B3O3 and pyridyl rings are colored pink. Blue polyhedra represent Zr. Grey, red, and pink spheres represent C/N, O, and B atoms, respectively.

Extended Data Fig. 3 Structure of MOF-406.

Extended structure of MOF-406 (a) and its corresponding linker 2D-L1 (b). B3O3 and pyridyl rings are colored pink. Blue polyhedra represent Zr. Grey, red, and pink spheres represent C/N, O, and B atoms, respectively.

Extended Data Fig. 4 Pore size and shape illustration of MOF-401‒405.

Interpenetrated MOF-401 (a) and MOF-402 (b) exhibit cylindrical pore channels; MOF-403 (c) contains two interconnected cage types; and each of MOF-404 (d) and MOF-405 (e) features two kinds of prismatic channels.

Supplementary information

Supplementary Information

Supplementary Figs. 1–48, Tables 1–10 and Discussion.

Supplementary Data 1

Source data for Supplementary Fig. 10.

Source data

Source Data Fig. 5

Source data for the adsorption and desorption isotherms in Fig. 5a and the micropore size distribution profiles in Fig. 5b.

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Liu, B., Wu, Y., Wang, L. et al. Covalent organic frameworks as infinite building units for metal–organic frameworks with compartmentalized pores. Nat. Chem. (2025). https://doi.org/10.1038/s41557-025-01953-2

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