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Issue 5, 2017
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Direct heteroarylation polymerization: guidelines for defect-free conjugated polymers

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Abstract

Direct (hetero)arylation polymerization (DHAP) has emerged as a valuable and atom-economical alternative to traditional cross-coupling methods for the synthesis of low-cost and efficient conjugated polymers for organic electronics. However, when applied to the synthesis of certain (hetero)arene-based materials, a lack of C–H bond selectivity has been observed. To prevent such undesirable side-reactions, we report the design and synthesis of new, bulky, phosphine-based ligands that significantly enhance selectivity of the DHAP process for both halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. To better understand the selectivity issues, density functional theory (DFT) calculations have been performed on various halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. Calculations showed that the presence of bromine atoms decreases the energy of activation (Ea) of the adjacent C–H bonds, allowing undesirable β-defects for some brominated aromatic units. Both calculations and the new ligands should lead to the rational design of monomers and methods for the preparation of defect-free conjugated polymers from DHAP.

Graphical abstract: Direct heteroarylation polymerization: guidelines for defect-free conjugated polymers

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Publication details

The article was received on 07 Feb 2017, accepted on 09 Mar 2017 and first published on 20 Mar 2017


Article type: Edge Article
DOI: 10.1039/C7SC00589J
Citation: Chem. Sci., 2017,8, 3913-3925
  • Open access: Creative Commons BY-NC license
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    Direct heteroarylation polymerization: guidelines for defect-free conjugated polymers

    T. Bura, S. Beaupré, M. Légaré, J. Quinn, E. Rochette, J. T. Blaskovits, F. Fontaine, A. Pron, Y. Li and M. Leclerc, Chem. Sci., 2017, 8, 3913
    DOI: 10.1039/C7SC00589J

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