Cathodic Polymerization through Electrochemical Dehalogenation

作者：Wang, Xiang; Wu, Jinghang; Liu, Hong; Kang, Fangyuan; Yan, Feng; Zhang, Qichun^*

来源：Macromolecules, 2023, 56(24): 10198-10205.

DOI：10.1021/acs.macromol.3c01154

• TRIFLUORIDE DIETHYL ETHERATE
• TRIFLUOROACETIC-ACID
• ARYL HALIDES
• POLY(P-PHENYLENE)
• ELECTROLYTE
• ANTHRACENE
• FRAMEWORK
• FILMS

It is very challenging to realize the polymerization of benzene/polycyclic aromatic hydrocarbons (PAHs) under neutral and mild conditions, although their polymerization could be harshly conducted. To address this issue, we envision that carbon-carbon coupling among small molecules can be fulfilled via electrochemical dehalogenation and believe that this method could become a general method for the polymerization of halogen-substituted benzene, halogen-substituted PAHs, or halogen-substituted heteroatom-containing aromatic compounds. In fact, employing electrons as catalysts to construct various conjugated polymers under mild and neutral conditions is very important to fabricate large-area thin films, as well as multilayer heterostructures for broad applications in organic optoelectronic devices. Here, we demonstrate that by employing the electrochemical dehalogenation method, 1,4-diiodo-(or dibromo)-benzene, 1,4-dibromonaphthalene, 1,5-dibromonaphthalene, 9,10-dibromoanthracene, 2,6-dibromoanthracene, 2,7-dibromophenanthrene, 2,7-dibromopyrene, 1,3,5-tribromobenzene, and 1,3,5-tris-(4-bromophenyl)-benzene can be polymerized at various cathodes (silicon, gold, platinum, stainless steel, etc.) to form smooth films, which has potential applications in organic optoelectrical devices.