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Photoinduced double hydrogen-atom transfer for polymerization and 3D printing of conductive polymer

Nature Synthesis volume 3, pages 1145–1157 (2024)Cite this article

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Abstract

The photoinduced polymerization of electron-rich heteroaromatic pentacycles (ERHPs), such as thiophene derivatives and pyrrole derivatives, is challenging owing to the inherent stability of their aromatic structure. The resultant polymers are organic semiconductor materials that are widely used in both organic electronic and bioelectronic devices. Here we report an efficient hydrogen-atom transfer (HAT) photocatalyst, which is the dimerization product (1,2-bis(4-(2-hydroxyethoxy)phenyl)ethane-1,2-dione) of an acyl radical generated by the photolysis of Irgacure 2959, and its use for the dehydrogenation of coupled ERHPs formed in an acidic environment. The dehydrogenation occurs via a double HAT process, enabling the photopolymerization of ERHPs. This reaction also allows us to fabricate three-dimensional (3D) conductive pathways in hydrogels. The hydrogel can be printed to form free-standing 3D conductive structures of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate with a precision of 220 nm, markedly surpassing structures built using previous methods (>10 µm). The approach introduces opportunities for precision engineering of 3D electrodes with the possibility of expanding applications in organic electronics and bioelectronics.

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Fig. 1: Traditional versus our approach for 3D printing of ERHP-based conductive structures.
Fig. 2: Characterization of the photoinduced polymerization of EDOT.
Fig. 3: Atmosphere control and radical inhibitor experiments.
Fig. 4: DFT calculations.
Fig. 5: Proposed mechanism for photoinduced polymerization of PEDOT:PSS.
Fig. 6: Characterization of the photoinduced polymerization of PEDOT:PSS.
Fig. 7: Photolithography of PEDOT:PSS micro–nano structure.

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All data to support the findings of this study are available within the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We gratefully acknowledge M. Wu and X. Zheng for their assistance with C-AFM measurements. We gratefully acknowledge Z. Wang for his assistance with the OLED preparation and characterization. We thank P. Sun for his assistance with the OSC preparation and characterization. We thank X. Xiao and J. Zhao for their help with nanosecond transient absorption measurements. All theoretical calculations were performed at the High-Performance Computing Center (HPCC) of Nanjing University. We acknowledge financial support from the National Natural Science Foundation of China (numbers 52033002, 22105035, 22122103, 22101130), the Natural Science Foundation of Jiangsu Province (numbers BK20210263, BK20211560), Fundamental Research Funds for the Central Universities (numbers 020514380304, 020514380252, 020514380272); J.H. acknowledges the support from the Xiaomi Foundation.

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Author notes

  1. These authors contributed equally: Xin Zhou, Shangwen Fang, Yangnan Hu.

Authors and Affiliations

  1. State Key Laboratory of Digital Medical Engineering, School of Biological Science and Medical Engineering, Southeast University, Nanjing, China

    Xin Zhou, Yangnan Hu, Xin Du, Haibo Ding, Renjie Chai & Zhongze Gu

  2. State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China

    Shangwen Fang, Jie Han & Jin Xie

  3. Department of Otolaryngology Head and Neck Surgery, Zhongda Hospital, School of Life Sciences and Technology, School of Medicine, Advanced Institute for Life and Health, Jiangsu Province High-Tech Key Laboratory for Bio-Medical Research, Southeast University, Nanjing, China

    Yangnan Hu & Renjie Chai

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Contributions

X.Z., Z.G., J.X. and J.H. conceived the work and designed the experiments. X.Z. and X.D. performed the synthesis and characterization of materials. X.Z. and H.D. conducted the 3D printing experiments. S.F. conducted experiments on the characterization of experimental mechanisms and proposed the catalytic cycle. J.H. performed the DFT calculations. Y.H. and R.C. performed cell experiments and analysed the data. The manuscript was written with contributions from all the authors.

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Correspondence to Jie Han, Jin Xie or Zhongze Gu.

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Nature Synthesis thanks Guoying Gu and the other, anonymous, reviewer(s) 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. 1–39, Discussion and Tables 1–3.

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Supplementary Video 1

Colour transition of electrochromic device under cyclic voltage.

Supplementary Video 2

Rapid and repeatable colour switching of electrochromic device.

Supplementary Data

Cartesian coordinates of optimized geometries.

Source data

Source Data Fig. 2

Statistical Source Data

Source Data Fig. 6

Statistical Source Data

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Zhou, X., Fang, S., Hu, Y. et al. Photoinduced double hydrogen-atom transfer for polymerization and 3D printing of conductive polymer. Nat. Synth 3, 1145–1157 (2024). https://doi.org/10.1038/s44160-024-00582-w

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