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Reversible formation and control of linear conjugation in polymers

Nature Chemistry volume 17, pages 1265–1274 (2025)Cite this article

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Abstract

The emergence of organic semiconductors has laid the foundation for the field of plastic electronics. Controlling π-conjugation by designing proper conjugated moieties is one of the commonest strategies for achieving desired semiconducting properties in conjugated materials. Despite significant advancements in the field, the reversible formation of extended conjugation to in situ switch the nature of macromolecules between semiconductors and insulators remains elusive. Here we disclose a generic strategy for developing polymeric structures that incorporate molecular switch units. These units enable the controlled activation and deactivation of linear conjugation in response to acid–base or electronic stimuli. This is achieved by copolymerizing non-π-conjugated lactone-functionalized xanthene moieties with traditional π-conjugated building blocks. With 2,6-dihydroxynaphthalene as an ‘electro-acid’, the electrochromic-like properties of these polymers were explored, demonstrating an effective in situ conversion of the non-conjugated, colourless polymers into conjugated, coloured polymers.

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Fig. 1: Design, synthesis and reversible control of the conjugation-tunable polymer.
Fig. 2: Systematic control of linear conjugation via fine-tuning of π-orbital overlap with various common aromatic moieties.
Fig. 3: Molecular structures of polymer models H-3bmodel–H-3dmodel optimized by DFT calculations.
Fig. 4: Electrical control of linear conjugation and resultant electrochromic-like behaviours.
Fig. 5: Mechanistic studies of polymer backbone reconfiguration in response to acid or electric stimuli.

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All data supporting the findings of this study are available in the main paper, Supplementary Information and source data files. Source data are provided with this paper.

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Acknowledgements

We are grateful for financial support from the Fundamental Research Funds for the Heilongjiang Universities (2022-KYYWF-1105). The funders had no role in study design, data collection and analysis, decision to publish or preparation of the manuscript. We thank J. Mei for valuable discussions during the revision of this paper.

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Author notes

  1. These authors contributed equally: Yanyun Wu, Jiongjiang Liu.

Authors and Affiliations

  1. Key Laboratory of Functional Inorganic Materials Chemistry (Ministry of Education) and School of Chemistry and Materials Science, Heilongjiang University, Harbin, China

    Yanyun Wu, Jiongjiang Liu, Mengya Wang, Wanan Cai, Haijun Niu & Kai Lang

  2. Printable Electronics Research Center, Nano Devices and Materials Division, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, China

    Xinzhou Wu

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Contributions

Y.W., J.L. and M.W. conducted the synthetic experiments. Y.W. carried out the materials characterization and device fabrication. J.L. performed the DFT calculations. X.W. and W.C. assisted with the project. K.L. conceived the work and directed the project. K.L. and H.N. directed the electrochromic studies. K.L., Y.W. and J.L. designed the experiments and wrote the paper.

Corresponding authors

Correspondence to Haijun Niu or Kai Lang.

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Competing interests

Heilongjiang University and K.L. Y.W., J.L. and M.W. have filed a patent (2024105595290) that covers aspects of the work reported in this paper. The other authors declare no competing interests.

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Nature Chemistry thanks Yan Xia 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 Figs. 1–34, discussion and Tables 1–10.

Supplementary Data

Coordinate data for Figs. 3 and 5.

Source data

Source Data Fig. 1

UV-absorption plot data.

Source Data Fig. 2

UV-absorption plot data.

Source Data Fig. 4

UV-absorption plot data.

Source Data Fig. 5

UV-absorption plot data.

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Wu, Y., Liu, J., Wang, M. et al. Reversible formation and control of linear conjugation in polymers. Nat. Chem. 17, 1265–1274 (2025). https://doi.org/10.1038/s41557-025-01851-7

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