Issue 5, 2017

Direct heteroarylation polymerization: guidelines for defect-free conjugated polymers

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

Supplementary files

Article information

Article type
Edge Article
Submitted
07 févr. 2017
Accepted
09 mars 2017
First published
20 mars 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2017,8, 3913-3925

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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