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Revealing polymerisation defects and formation mechanisms in aldol condensation for conjugated polymers via high-resolution molecular imaging

Author

Listed:
  • Xiaocui Wu

    (University of Warwick
    Université de Lorraine)

  • Stefania Moro

    (University of Birmingham)

  • Adam Marks

    (University of Oxford
    Stanford University)

  • Maryam Alsufyani

    (University of Oxford
    Massachusetts Institute of Technology)

  • Zidi Yu

    (Peking University)

  • Luís M. A. Perdigão

    (University of Warwick)

  • Xingxing Chen

    (Anhui University)

  • Alexander M. T. Luci

    (University of Warwick)

  • Callum Crockford

    (University of Warwick)

  • Simon E. F. Spencer

    (University of Warwick)

  • David J. Fox

    (University of Warwick)

  • Jian Pei

    (Peking University)

  • Iain McCulloch

    (University of Oxford
    Princeton University)

  • Giovanni Costantini

    (University of Birmingham
    University of Birmingham)

Abstract

Aldol condensation is a crucial synthetic reaction in organic chemistry, particularly valued for fabricating conjugated polymers without the use of metals or toxic organostannanes. However, due to the lack of reliable and precise analytical methods, no direct evidence of the microstructure and sequence of synthesised polymers has been obtained, limiting control over their structure and performance. Here, by combining electrospray deposition and scanning tunnelling microscopy (ESD-STM), we analyse sub-monomer resolution images of four different n-type polymers produced via aldol condensation, revealing unexpected defects in both the sequence of (co)monomers and their coupling. These defects, observed across all polymer samples, indicate alternative side reaction pathways inherent to aldol condensation. Our findings not only uncover the reaction mechanism responsible for these defects but also bring new insights for the design of more effective synthetic pathways to minimise structural defects in conjugated polymers.

Suggested Citation

  • Xiaocui Wu & Stefania Moro & Adam Marks & Maryam Alsufyani & Zidi Yu & Luís M. A. Perdigão & Xingxing Chen & Alexander M. T. Luci & Callum Crockford & Simon E. F. Spencer & David J. Fox & Jian Pei & I, 2025. "Revealing polymerisation defects and formation mechanisms in aldol condensation for conjugated polymers via high-resolution molecular imaging," Nature Communications, Nature, vol. 16(1), pages 1-8, December.
  • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-62221-y
    DOI: 10.1038/s41467-025-62221-y
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