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Adaptive metal–organic frameworks with crystalline dynamicity for durable gas separation

Nature Synthesis volume 5, pages 129–138 (2026)Cite this article

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Abstract

Dynamic chemistry offers opportunities for the design of smart materials that can self adapt or self repair to mediate their functionality. However, achieving anti-crack toughness using dynamic covalent bonds is often overlooked in crystalline porous solids such as metal–organic frameworks. Here we propose that crystalline dynamicity can be derived from bio-inspired disulfide metathesis, as demonstrated by a dynamic combinatorial library of isomeric metal–organic frameworks (LIFM-105, LIFM-105i, and LIFM-105a). Sulfur–sulfur bond breakage and regeneration facilitate stimuli-responsive interconversion between two-dimensional and three-dimensional frameworks, involving simultaneous layer rotation, component shift and linkage reorganization. The disulfide exchange-based crystal dynamics provides these porous solids with gas-induced adaptiveness and the gate effect, enabling pore tuning for efficient removal of C2H2 from C2H4. Additionally, the guest-adaptation-motivated restoration and reorganization of the ‘damaged’ frameworks afford a promising protocol to apply radical-mediated dynamic solids as adaptive porous materials for durable separation and other applications.

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Fig. 1: Disulfide metathesis-mediated dynamic combinatorial library of MOFs.
Fig. 2: Structural comparison of LIFM-105, LIFM-105a and LIFM-105·C2H2.
Fig. 3: Structural transformation and radical identification.
Fig. 4: Gas adsorption and separation study.
Fig. 5: Energy schematic diagram for structural conversion and regeneration.

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Data availability

Crystallographic data for the structures in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition numbers CCDC 1919410 (LIFM-105-100 K), 2440073 (LIFM-105-298 K), 2440074 (LIFM-105-308 K), 2373234 (LIFM-105i), 1919412 (LIFM-105a) and 1919414 (LIFM-105 C2H2). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. The data that support the conclusions in the paper are present in the Article or its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the NKRD Program of China (2021YFA1500401) (C.-Y.S.), the NSFC (92461302, 22471294) (C-.Y.S., C.-X.C.), Guangdong Introducing Innovative and Entrepreneurial Teams (2023ZT10L061) (C.-X.C.) and the Robert A. Welch Foundation (B0027) (S.M.). C.-X.C. thanks Y. Ye for his help in in situ gas-loading-dependent PXRD experiments.

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Authors and Affiliations

  1. MOE Laboratory of Bioinorganic and Synthetic Chemistry, GBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen University, Guangzhou, China

    Cheng-Xia Chen, Yang-Yang Xiong, Zhang-Wen Wei & Cheng-Yong Su

  2. Department of Chemistry, University of North Texas, Denton, TX, USA

    Cheng-Xia Chen, Pui Ching Lan, Kui Tan & Shengqian Ma

  3. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, China

    Xili Cui & Lifeng Yang

  4. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, China

    Zheng Niu

  5. Department of Chemistry, University of South Florida, Tampa, FL, USA

    Chuan Shan

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  1. Cheng-Xia Chen
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  2. Xili Cui
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Contributions

C.-Y.S. conceived and coordinated the project. C.-X.C. and S.M. designed the experiments. C.-X.C. carried out the syntheses and measurements. C.-X.C. and K.T. performed the in situ IR experiments. C.-Y.S., S.M. and C.-X.C wrote the manuscript. P.C.L., Z.-W.W. and Y.Y.X. helped in experiments. X.C. and L.Y. performed the theoretical calculation. C.-X.C., Z.N., Z.-W.W. and C.S. performed the crystal analyses.

Corresponding authors

Correspondence to Shengqian Ma or Cheng-Yong Su.

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The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Jun Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information (download PDF )

Supplementary Figs. 1–88, Tables 1–7, methods, discussions and references.

Supplementary Data 1

Crystallographic data for LIFM-105-100 K, CCDC 1919410.

Supplementary Data 2

Crystallographic data for LIFM-105-298 K, CCDC 2440073.

Supplementary Data 3

Crystallographic data for LIFM-105-308 K, CCDC 2440074.

Supplementary Data 4

Crystallographic data for LIFM-105i, CCDC 2373234.

Supplementary Data 5

Crystallographic data for LIFM-105a, CCDC 1919412.

Supplementary Data 6

Crystallographic data for LIFM-105 C2H2, CCDC 1919414.

Source data

Source Data Fig. 1 (download XLSX )

EPR data for LIFM-105.

Source Data Fig. 3 (download XLSX )

VT-PXRD, time-dependent PXRD and EPR data for LIFM-105.

Source Data Fig. 4 (download XLSX )

Data for C2H2 and C2H4 adsorption and C2H2/C2H4 breakthrough experiments.

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Chen, CX., Cui, X., Xiong, YY. et al. Adaptive metal–organic frameworks with crystalline dynamicity for durable gas separation. Nat. Synth 5, 129–138 (2026). https://doi.org/10.1038/s44160-025-00911-7

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