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Cryogenically self-healing organic crystals

Nature Materials (2025)Cite this article

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Abstract

Common self-healing mechanisms rely on the diffusion of chemical entities across a fissure to rebuild the interface. As diffusion is temperature-controlled, cryogenic conditions are prohibitive to self-healing. Here we report a molecular crystal that heals at ambient and high temperature (298 and 423 K) but that is also capable of autonomous recovery at 77 K. The efficiency of this process depends on dipole–dipole interactions as the dominant mechanism that reduces the separation between the interfaces. Comparative optical transmission measurements confirm that healed crystals are approximately 99% transparent relative to the same material before cracking. This cryogenic self-healing capability is used to design an autonomously reparative, all-organic, crystalline optical transmission system and enables substantial recovery of the optical losses due to the material’s ability to recover after damage. This and possibly other similar materials overcome the natural limitations of macromolecular self-healing media at cryogenic temperatures, opening opportunities for developing materials that can operate practically indefinitely under extreme conditions.

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Fig. 1: Structure and self-healing of PBDPA crystals at different temperatures.
Fig. 2: Surface topography of crystals that self-healed at room temperature.
Fig. 3: Crystal structure and electronic properties of PBDPA.
Fig. 4: Sample preparation and KPFM surface potential mapping of fractured PBDPA crystals.
Fig. 5: Optical transmission and loss recovery in PBDPA crystals.

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Data availability

The crystallographic information for PBDPA has been deposited at the Cambridge Crystallographic Data Centre under deposition nos. 2414673 (298 K) and 2414674 (100 K). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.

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Acknowledgements

This work received support from the National Natural Science Foundation of China (grant nos. 52373181 and 52173164), the Natural Science Foundation of Jilin Province (grant no. 20230101038JC) and funding from New York University Abu Dhabi (project AD073). Additionally, this material is based on works supported by Tamkeen under NYUAD RRC grant no. CG011.

Author information

Authors and Affiliations

  1. State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, P. R. China

    Chengde Ding, Baolei Tang, Yuxing Zhou, Bowen Jin & Hongyu Zhang

  2. Smart Materials Lab, New York University Abu Dhabi, Abu Dhabi, UAE

    Patrick Commins, Marieh B. Al-Handawi, Liang Li & Panče Naumov

  3. SAFIR Novel Materials Development Lab, Sorbonne University Abu Dhabi, Abu Dhabi, UAE

    Liang Li

  4. Center for Smart Engineering Materials, New York University Abu Dhabi, Abu Dhabi, UAE

    Panče Naumov

  5. Research Center for Environment and Materials, Macedonian Academy of Sciences and Arts, Skopje, Macedonia

    Panče Naumov

  6. Molecular Design Institute, Department of Chemistry, New York University, New York, NY, USA

    Panče Naumov

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  1. Chengde Ding
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  2. Baolei Tang
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Contributions

H.Z., L.L. and P.N. conceived of the project. C.D., B.T., Y.Z. and B.J. performed the experiments. P.C., M.B.A. and H.Z. supervised the experiments. B.T., H.Z. and P.N. cowrote the manuscript.

Corresponding authors

Correspondence to Panče Naumov or Hongyu Zhang.

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The authors declare no competing interests.

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Nature Materials thanks Christopher Bardeen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Notes 1–5. Figs. 1–28. Tables 1–5 and References.

Supplementary Video 1

Fast self-healing process of PBDPA crystals.

Supplementary Video 2

Gradual self-healing process of PBDPA crystals.

Supplementary Video 3

Applying a longitudinal force parallel to the (001) plane induces healing of PBDPA crystals.

Supplementary Video 4

Applying a lateral force perpendicular to the (001) plane induces healing of PBDPA crystals.

Supplementary Video 5

Self-healing process of PBDPA crystals at 423 k.

Supplementary Video 6

Self-healing process of PBDPA crystals at 77 k (Sample 1).

Supplementary Video 7

Self-healing process of PBDPA crystals at 77 k (Sample 2).

Supplementary Video 8

PBDPA crystals used for AFM testing after self-healing.

Supplementary Video 9

PBDPA crystals used for CLSM testing after self-healing.

Supplementary Data 1

Source data for supplementary information.

Supplementary Data 2

Crystallographic data of PBDPA crystals at 100 K.

Supplementary Data 3

Crystallographic data of PBDPA crystals at 298 K.

Source data

Source Data Fig. 4

Source data for Fig. 4.

Source Data Fig. 5

Source data for Fig. 5.

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Ding, C., Tang, B., Zhou, Y. et al. Cryogenically self-healing organic crystals. Nat. Mater. (2025). https://doi.org/10.1038/s41563-025-02411-7

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