Influence of Bromo-Aromatic Substrates on Direct Arylation of EDOTs toward Higher Molecular Conjugate Polymer

Xi-Lin Pei; Quan Yang; Yan-Lu Sun; Wei Wu; Jian-Yong Yu; Yong He

doi:10.1007/s10118-025-3327-5

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Influence of Bromo-Aromatic Substrates on Direct Arylation of EDOTs toward Higher Molecular Conjugate Polymer

RESEARCH ARTICLE | Updated：2025-07-14

- Influence of Bromo-Aromatic Substrates on Direct Arylation of EDOTs toward Higher Molecular Conjugate Polymer
- Chinese Journal of Polymer Science Vol. 43, Issue 5, Pages: 718-729(2025)
- Affiliations：
  
  a.State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
  b.Innovation Center for Textile Science and Technology, Donghua University, Shanghai 201620, China
  c.School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
- Author bio：
  
  yhe@dhu.edu.cn
- Funds：
- DOI：10.1007/s10118-025-3327-5
  CLC：
- Received：11 November 2024，
  
  Revised：23 January 2025，
  
  Accepted：26 February 2025，
  
  Published Online：10 April 2025，
  
  Published：30 April 2025
- Accepted：
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Pei, X. L.; Yang, Q.; Sun, Y. L.; Wu, W.; Yu, J. Y.; He, Y. Influence of bromo-aromatic substrates on direct arylation of EDOTs toward higher molecular conjugate polymer. Chinese J. Polym. Sci. 2025, 43, 718–729

Xi-Lin Pei, Quan Yang, Yan-Lu Sun, et al. Influence of Bromo-Aromatic Substrates on Direct Arylation of EDOTs toward Higher Molecular Conjugate Polymer[J]. Chinese journal of polymer science, 2025, 43(5): 718-729.
Pei, X. L.; Yang, Q.; Sun, Y. L.; Wu, W.; Yu, J. Y.; He, Y. Influence of bromo-aromatic substrates on direct arylation of EDOTs toward higher molecular conjugate polymer. Chinese J. Polym. Sci. 2025, 43, 718–729 DOI： 10.1007/s10118-025-3327-5.

Xi-Lin Pei, Quan Yang, Yan-Lu Sun, et al. Influence of Bromo-Aromatic Substrates on Direct Arylation of EDOTs toward Higher Molecular Conjugate Polymer[J]. Chinese journal of polymer science, 2025, 43(5): 718-729. DOI： 10.1007/s10118-025-3327-5.

摘要

Bromo-aromatics substrate-controlled electrophilicity modulation for enhanced EDOT activation.

Abstract

The influence of the electronic and steric properties of bromoaromatic substrates on direct arylation polymerization for synthesizing high-molecular-weight conjugated polymers was investigated through a combination of experiments and calculations. Bromo-aromatic substrates with electron-withdrawing fluoro substituents exhibited higher yields and degrees of polymerization under PPh

-assisted conditions compared to those with electron-donating or bulky methyl substituents. Additionally

excessive steric hindrance at ortho-sites or overly electron-deficient dibromoaromatic substrates leads to reaction inactivation. Calculations indicated that electron-withdrawing substituents enhanced the electrophilicity of arylpalladium-PPh

intermediates

facilitating the activation of electron-rich arylative substrates and promoting polymer growth. Furthermore

steric hindrance from the substituents can influence the preferred reaction pathway

thereby increasing the real reaction barriers. Both experimental and computational results suggest that bromoaromatic substrates with optimized electron-deficient characteristics significantly improve monomer conversion and polymerization efficiency with

-hexylmethylether-substituted EDOT. These findings clarify how the electronic and steric properties of bromo-aromatic substrates affect EDOT derivative activation and are expected to aid in optimizing the polymerization conditions for the preparation of high-molecular-weight conjugated polymers.

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references

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