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General room-temperature Suzuki–Miyaura polymerization for organic electronics

Nature Materials (2024)Cite this article

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Abstract

π-Conjugated polymers (CPs) have broad applications in high-performance optoelectronics, energy storage, sensors and biomedicine. However, developing green and efficient methods to precisely synthesize alternating CP structures on a large scale remains challenging and critical for their industrialization. Here a room-temperature, scalable and homogeneous Suzuki–Miyaura-type polymerization reaction is developed with broad generality validated for 24 CPs including donor–donor, donor–acceptor and acceptor–acceptor connectivities, yielding device-quality polymers with high molecular masses. Furthermore, the polymerization protocol significantly reduces homocoupling structural defects, yielding more structurally regular and higher-performance electronic materials and optoelectronic devices than conventional thermally activated polymerizations. Experimental and theoretical studies reveal that a borate transmetalation process plays a key role in suppressing protodeboronation, which is critical for large-scale structural regularity. Thus, these results provide a general polymerization tool for the scalable production of device-quality CPs with alternating structural regularity.

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Fig. 1: Suzuki–Miyaura polymerization to access π-CPs.
Fig. 2: Mechanistic study results.
Fig. 3: Investigation of the practical uniformity and scalability of the present polymerization protocol.
Fig. 4: Homocoupling defect analysis.

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Data availability

All relevant data supporting the findings of this study are available in the Article and its Supplementary Information. Synthesis procedures and characterization for all the new compounds, computational studies and all copies of NMR spectra and gel permeation chromatography traces are available in the Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We acknowledge financial support from the NSFC (51925306 (H.H.), 52222309 (Q.S.) and 52173187 (Q.S.)), National Key R&D Program of China (2018FYA 0305800 (H.H.)), Key Research Program of the Chinese Academy of Sciences (XDPB08-2 (H.H.)), China Postdoctoral Science Foundation (2021M703158 (H.X.)) and Fundamental Research Funds for the Central University. T.J.M. thanks the National Science Foundation Materials Research Science and Engineering Center at Northwestern University (DMR-2308691) and the Air Force Office of Scientific Research (FA9550-22-1-0423) for support. We thank X. Hao and J. Qiao from Shandong University for the exciton diffusion length measurements.

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Authors and Affiliations

  1. College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, People’s Republic of China

    Haigen Xiong, Qijie Lin, Song Wang, Wenbin Xie, Congqi Li, Xin Zhang, Qinqin Shi & Hui Huang

  2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, People’s Republic of China

    Haigen Xiong, Qinqin Shi & Hui Huang

  3. School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, People’s Republic of China

    Yu Lu, Yawen Li, Yuze Lin & Zhi-Xiang Wang

  4. Department of Chemistry and the Materials Research Center, Northwestern University, Evanston, IL, USA

    Ding Zheng & Tobin J. Marks

  5. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, People’s Republic of China

    Yawen Li & Yuze Lin

  6. CAS Center for Excellence in Topological Quantum Computation, University of Chinese Academy of Sciences, Beijing, People’s Republic of China

    Hui Huang

  7. CAS Key Laboratory of Vacuum Physics, University of Chinese Academy of Sciences, Beijing, People’s Republic of China

    Hui Huang

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Contributions

H.H. directed the investigations and provided overall supervision. H.X. designed the experiments. H.X., W.X., X.Z. and Q.S. performed the synthesis experiments. Q.L. and D.Z. performed the device fabrications. Y. Lu, S.W. and Z.W. performed the DFT calculations. Y. Li and Y. Lin performed the trap density measurements. S.W., C.L. and X.Z. performed the atomic force microscopy and GIWAXS measurements. H.X., Q.S., T.J.M. and H.H. prepared the manuscript.

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Correspondence to Qinqin Shi, Tobin J. Marks or Hui Huang.

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Xiong, H., Lin, Q., Lu, Y. et al. General room-temperature Suzuki–Miyaura polymerization for organic electronics. Nat. Mater. (2024). https://doi.org/10.1038/s41563-023-01794-9

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