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

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...

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Main Authors: 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, Iain McCulloch, Giovanni Costantini
Format: Article
Language:English
Published: Nature Portfolio 2025-07-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-62221-y
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author 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
Iain McCulloch
Giovanni Costantini
author_facet 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
Iain McCulloch
Giovanni Costantini
author_sort Xiaocui Wu
collection DOAJ
description 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.
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spelling doaj-art-ae9e69c5d3864a4886032d1ab1ee82fa2025-08-20T03:05:06ZengNature PortfolioNature Communications2041-17232025-07-011611810.1038/s41467-025-62221-yRevealing polymerisation defects and formation mechanisms in aldol condensation for conjugated polymers via high-resolution molecular imagingXiaocui Wu0Stefania Moro1Adam Marks2Maryam Alsufyani3Zidi Yu4Luís M. A. Perdigão5Xingxing Chen6Alexander M. T. Luci7Callum Crockford8Simon E. F. Spencer9David J. Fox10Jian Pei11Iain McCulloch12Giovanni Costantini13Department of Chemistry, University of WarwickSchool of Chemistry, University of BirminghamDepartment of Chemistry, University of OxfordDepartment of Chemistry, University of OxfordCollege of Chemistry and Molecular Engineering, Peking UniversityDepartment of Chemistry, University of WarwickDepartment of Materials, School of Chemistry & Chemical Engineering, Anhui UniversityDepartment of Chemistry, University of WarwickDepartment of Chemistry, University of WarwickDepartment of Statistics, University of WarwickDepartment of Chemistry, University of WarwickCollege of Chemistry and Molecular Engineering, Peking UniversityDepartment of Chemistry, University of OxfordSchool of Chemistry, University of BirminghamAbstract 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.https://doi.org/10.1038/s41467-025-62221-y
spellingShingle 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
Iain McCulloch
Giovanni Costantini
Revealing polymerisation defects and formation mechanisms in aldol condensation for conjugated polymers via high-resolution molecular imaging
Nature Communications
title Revealing polymerisation defects and formation mechanisms in aldol condensation for conjugated polymers via high-resolution molecular imaging
title_full Revealing polymerisation defects and formation mechanisms in aldol condensation for conjugated polymers via high-resolution molecular imaging
title_fullStr Revealing polymerisation defects and formation mechanisms in aldol condensation for conjugated polymers via high-resolution molecular imaging
title_full_unstemmed Revealing polymerisation defects and formation mechanisms in aldol condensation for conjugated polymers via high-resolution molecular imaging
title_short Revealing polymerisation defects and formation mechanisms in aldol condensation for conjugated polymers via high-resolution molecular imaging
title_sort revealing polymerisation defects and formation mechanisms in aldol condensation for conjugated polymers via high resolution molecular imaging
url https://doi.org/10.1038/s41467-025-62221-y
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