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Catenated covalent organic frameworks constructed from polyhedra

Nature Synthesis volume 2, pages 286–295 (2023)Cite this article

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Abstract

Although the synthetic chemistry leading to interlocking molecular [n]catenanes of organic polyhedra (n = 2–3) and rings (n = 2–130) is established, the analogous chemistry that pertains to infinite three-dimensional systems ([∞]catenane) remains undeveloped. We report a series of [∞]catenane covalent organic frameworks (termed catena-COFs). These were synthesized by linking 4,4′-(1,10-phenanthroline-2,9-diyl)dibenzaldehyde to either of tris-(4-aminophenyl)-amine, -methane or -methanol through imine condensation. These combinations give discrete adamantane-like polyhedra, catenated by virtue of the copper(I) ions templating a mutually embracing arrangement of PDBs (points-of-catenation), which ultimately results in infinite catena-COF-805, 806 and 807. The crystal structures of these COFs obtained from electron microscopy and X-ray diffraction were determined to be isoreticular and to adopt the bor-y structure type.

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Fig. 1: Synthetic strategy and design of the 3D [∞]catenane COFs.
Fig. 2: Perspectives of the crystal structure of catena-COF-805.
Fig. 3: TEM data and perspective illustrations of the crystal structure of catena-COF-805.
Fig. 4: TEM data and perspective illustrations of the crystal structure of catena-COF-806.
Fig. 5: PXRD refinement and crystal structures of 3D [∞]catenane COFs.

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Data availability

Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2216102 (catena-COF-805), 2216103 (catena-COF-806) and 2216104 (catena-COF-807). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All data are available in the main text or the Supplementary Information.

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Acknowledgements

This research was partly supported by King Abdulaziz City for Science and Technology (Center of Excellence for Nanomaterials and Clean Energy Applications), and mechanical property measurements funded by the Defense Advanced Research Projects Agency (DARPA) under contract HR001-119-S-0048. This research used resources of the Advanced Light Source (beamline 7.3.3) at Lawrence Berkeley National Laboratory, which is a DOE Office of Science user facility under contract DE-AC02-05CH11231. Y.Z. and O.T. acknowledge the support of the Center for High-resolution Electron Microscopy (CℏEM), ShanghaiTech University (EM02161943), Shanghai Science and Technology Plan (21DZ2260400) and National Natural Science Foundation of China (21835002). We thank C. Zhu for assistance in acquiring synchrotron PXRD data on beamline 7.3.3 of the Advanced Light Source, A. Lund and H. Celik of the School of Chemical Sciences at the University of California-Berkeley NMR facility for assistance with solid-state NMR data acquisition, Z. Wang at the Cornell High Energy Synchrotron Source and T. Matsumoto and A. Yamano at the Rigaku Co., Japan, for the initial trials on acquiring single-crystal XRD and PXRD data. D.M.P. thanks V. A. Blatov at the Samara Center for Theoretical Materials Science for providing the ToposPro software.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of California, Berkeley, CA, USA

    Tianqiong Ma, Christian S. Diercks, Hao Lyu, Nikita Hanikel, Yuzhong Liu, Nicolas J. Diercks & Omar M. Yaghi

  2. Kavli Energy NanoScience Institute, Berkeley, CA, USA

    Tianqiong Ma, Christian S. Diercks, Hao Lyu, Nikita Hanikel, Yuzhong Liu, Nicolas J. Diercks & Omar M. Yaghi

  3. Bakar Institute of Digital Materials for the Planet, Division of Computing, Data Science, and Society, University of California, Berkeley, CA, USA

    Tianqiong Ma, Christian S. Diercks, Hao Lyu, Nikita Hanikel, Yuzhong Liu, Nicolas J. Diercks & Omar M. Yaghi

  4. Center for High-Resolution Electron Microscopy (CℏEM), School of Physical Science and Technology, ShanghaiTech University, Shanghai, People’s Republic of China

    Yi Zhou & Osamu Terasaki

  5. Shanghai Key Laboratory of High-Resolution Electron Microscopy, ShanghaiTech University, Shanghai, People’s Republic of China

    Yi Zhou & Osamu Terasaki

  6. Department of Mechanical Engineering, University of California, Berkeley, CA, USA

    Junpyo Kwon & Robert O. Ritchie

  7. Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Junpyo Kwon & Robert O. Ritchie

  8. Department of New Architectures in Materials Chemistry, Materials Science Institute of Madrid, Consejo Superior de Investigaciones Científicas, Madrid, Spain

    Felipe Gándara & Pilar Pena-Sánchez

  9. Department of Materials Science and Engineering, University of California, Berkeley, CA, USA

    Robert O. Ritchie

  10. Dipartimento di Chimica, Università degli studi di Milano, Milano, Italy

    Davide M. Proserpio

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  1. Tianqiong Ma
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Contributions

C.S.D., T.M. and O.M.Y. conceived the idea. T.M. and O.M.Y. led the project and interpreted the results. T.M. conducted the syntheses, structure analyses and characterizations for all the samples and interpreted the data. Y.Z. and O.T. collected and analysed the TEM data, and supported the comparison of TEM and PXRD results. J.K. and R.O.R. collected and analysed the nanoindentation data. F.G. and P.P.S. finalized the PXRD refinement. H.L. and Y.Z. supported the scanning electron microscopy measurements. N.H. conducted the THF sorption experiment. Y.L. and N.J.D. supported the linker synthesis. D.M.P. helped in the literature and topological analysis of the organic polyhedra and catenation. T.M., C.S.D. and O.M.Y. wrote the manuscript and all the authors reviewed it.

Corresponding author

Correspondence to Omar M. Yaghi.

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Nature Synthesis thanks the anonymous reviewers 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 Figs. 1–57, Tables 1–5 and Scheme 1.

Supplementary Data 1

Crystal structure of catena-COF-805; CCDC 2216102.

Supplementary Data 2

Crystal structure of catena-COF-806; CCDC 2216103.

Supplementary Data 3

Crystal structure of catena-COF-807; CCDC 2216104.

Source data

Source Data Fig. 5

Experimental PXRD data of catena-COF-805 and -806.

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Ma, T., Zhou, Y., Diercks, C.S. et al. Catenated covalent organic frameworks constructed from polyhedra. Nat. Synth 2, 286–295 (2023). https://doi.org/10.1038/s44160-022-00224-z

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