En Route to Defect-Free Polythiophene Derivatives by Direct Heteroarylation Polymerization

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• 作者：Thomas Bura ; Pierre-Olivier Morin ; Mario Leclerc
• 刊名：Macromolecules
• 出版年：2015
• 出版时间：August 25, 2015
• 年：2015
• 卷：48
• 期：16
• 页码：5614-5620
• 全文大小：411K
• ISSN：1520-5835

文摘

We report the synthesis of well-defined poly(3,3鈥?didodecyl-2,2鈥?5鈥?2鈥?5鈥?2鈥?quaterthiophene) (PQT12) from a direct heteroarylation polymerization (DHAP) of 5-bromo-3,3鈥?didodecyl-2,2鈥?5鈥?2鈥?5鈥?2鈥?quaterthiophene (monomer A) and 5-bromo-3鈥?4鈥?didodecyl-2,2鈥?5鈥?2鈥?5鈥?2鈥?quaterthiophene (monomer B). Experiments with different catalysts, ligands, additives, and solvents have revealed that the utilization of Herrmann鈥揃eller catalyst and P(o-NMe₂Ph)₃ can lead to selective thiophene鈥搕hiophene couplings. In this regard, solid-state optical and thermal measurements were particularly useful to detect the presence of 尾-branching and indicate that minor molecular defects can induce important changes within the supramolecular organization. We also highlight the fact that steric protection around unsubstituted 尾-positions of 伪-bromothiophene units is needed to obtain a good selectivity of the cross-couplings at the 伪-positions. This can be achieved by the presence of a substituent at an adjacent 尾-position or the utilization of a bulky acidic additive (i.e., neodecanoic acid) in the catalytic system. These synthetic procedures applied to both monomers have led to PQT12 samples showing essentially the same optical and thermal properties and are comparable to those observed with their analogues prepared from chemical oxidation or Stille coupling.