화학공학소재연구정보센터
Macromolecules, Vol.54, No.2, 725-735, 2021
Diversification of Conjugated Polymers via Postpolymerization Nucleophilic Aromatic Substitution Reactions with Sulfur-, Oxygen-, and Nitrogen-Based Nucleophiles
A postpolymerization nucleophilic aromatic substitution reaction is used as a strategy to efficiently diversify conjugated polymers. Conjugated polymers and small molecular models bearing tetrafluorophenyl and octafluorobiphenyl units are reacted with thiophenol derivatives, phenol derivatives, and carbazole in the presence of bases. Model reactions provide insights into the reactivity, numbers and patterns of substitution, structural features, and spectroscopic data. Thiophenol derivatives and carbazole achieve complete substitution of fluorine atoms in both the polymer and the model reactions, whereas phenol derivatives result in disubstitution in each arene ring with para-selectivity. The highly twisted and structurally rigid main chain structures are confirmed for a fully substituted arene motif in both the polymers and the models, resulting in the formation of syn- and anti-atropisomer or axial chirality and in the twisted intramolecular charge transfer character. The obtained polymers and models show unique optical and electrochemical properties, including phosphorescence at low temperatures in the case of the sulfur-containing materials.