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A solution processible single-crystal porous organic polymer

Nature Synthesis volume 2, pages 873–879 (2023)Cite this article

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Abstract

Synthetic organic polymers are typically insoluble polycrystalline or amorphous products rather than single crystals. Here we demonstrate that covalent polymer chains can achieve single-crystal form through the rational design of their hierarchical structure. Single-crystal X-ray diffraction analysis reveals that the polycondensation of 1,4-phenylenebisboronic acid yields a B4O52− cluster-based tetramer, which further extends into one-dimensional covalent chains that are physically crosslinked by hydrogen bonds and electrostatic interactions. These interactions ultimately afford a single crystal porous framework denoted as PHOF-1. Cryogenic electron microscopy and gel permeation chromatography studies indicate that the dissolved PHOF-1 maintains the consecutive one-dimensional chain structure with a very narrow molecular weight distribution. This solution processibility enables the continuous coating PHOF-1 onto a non-woven fabric to afford a composite textile capable of capturing NH3. The design strategy may open an avenue for the exploration of single-crystal porous polymer materials with precise structural information, confined pore spaces and straightforward solution processibility.

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Fig. 1: Synthesis route of PHOF-1.
Fig. 2: Hierarchical structure of PHOF-1.
Fig. 3: Stability and porosity of PHOF-1.
Fig. 4: Synthesis and reversible transformation of PHOF-1.
Fig. 5: NH3 capture performance of PHOF-1.
Fig. 6: Solution-processed PHOF-1 coating on fabrics.

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Data availability

Experimental data, characterization data and crystallographic data are provided in Supplementary Information. Meanwhile, the X-ray crystallographic data for PHOF-1, PHOF-1-Re and PHOF-1-NH3 have also been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition nos. 2088646, 2088647 and 2239634, which can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk.

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Acknowledgements

We gratefully acknowledge the financial support from National Key Research and Development Program of China (2018YFA0208600, T.-F.L.), National Natural Science Foundation of China (22033008, R.C.), CAS-Iranian Vice Presidency for Science and Technology Joint Research Project (121835KYSB20200034, T.-F.L) and Fujian Science Technology Innovation Laboratory for Optoelectronic Information of China (2021ZR105, T.-F.L). K.O.K. gratefully acknowledges support from the IIN Postdoctoral Fellowship and the Northwestern University International Institute for Nanotechnology. We thank J. Yue and B. Guan of the Institute of Chemistry (Chinese Academy of Sciences) for the cryo-TEM measurements. We thank Z. Xiong for the birefringence experiment and Q. Yin for the SC-XRD data collection.

Author information

Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, China

    Bai-Tong Liu, Sheng-Hao Gong, Xiao-Tian Jiang, Yuan Zhang, Rui Wang, Shuo Zhang, Tian-Fu Liu & Rong Cao

  2. University of Chinese Academy of Sciences, Beijing, China

    Bai-Tong Liu, Tian-Fu Liu & Rong Cao

  3. Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, IL, USA

    Zhijie Chen, Kent O. Kirlikovali & Omar K. Farha

  4. Fujian Science Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, China

    Tian-Fu Liu

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Contributions

T.-F.L., O.K.F. and R.C. guided the project. B.-T.L. designed and carried out most of the synthesis and characterizations in this work. S.-H.G. and R.W assisted the synthetic experiment. X.-T.J. assisted the TEM image measurement. Y.Z. assisted the SEM image measurement. Z.C. conducted the experiments on NH3 adsorption and separation. S.Z. assisted the in situ FT-IR spectra testing. B.-T.L. finished the manuscript, K.O.K. helped with editing and T.-F.L., O.K.F. and R.C. commented and revised on the manuscript.

Corresponding authors

Correspondence to Tian-Fu Liu, Omar K. Farha or Rong Cao.

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The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Sheng Dai, Shengqian Ma and Soumya Mukherjee 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. 1–32, discussion and Tables 1–8.

Supplementary Video 1

Regeneration process of PHOF-1.

Supplementary Video 2

Stability of PHOF-1 in different solvents.

Supplementary Video 3

Stability of PHOF-1 in acidic solution.

Supplementary Crystallographic

Data 1 for PHOF-1 Crystal data of PHOF-1, CCDC 2088646.

Supplementary Crystallographic

Data 2 for PHOF-1-Re Crystal data of PHOF-1-Re, CCDC 2088647.

Supplementary Crystallographic Data

Supplementary Crystallographic Data 3 for PHOF-1-NH3 Crystal data of PHOF-1-NH3, CCDC 2239634.

Source data

Source Data Fig. 3

Source data of PXRD patterns and adsorption isotherms.

Source Data Fig. 4

Source data of optical microscope images and cryo-EM image.

Source Data Fig. 5

Source data of NH3 adsorption–desorption isotherms and NH3 breakthrough curves.

Source Data Fig. 6

Source data of SEM image and EDS carbon and boron elemental mapping images.

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Liu, BT., Gong, SH., Jiang, XT. et al. A solution processible single-crystal porous organic polymer. Nat. Synth 2, 873–879 (2023). https://doi.org/10.1038/s44160-023-00316-4

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