Eco-friendly synthesis of ionic helical polymers and their chemical properties and reactivity

Isao Yamaguchi; Yuki Tanaka; Aohan Wang

doi:10.1039/c8ra05686b

Eco-friendly synthesis of ionic helical polymers and their chemical properties and reactivity

RSC Adv. 2018 Aug 24;8(52):29988-29994. doi: 10.1039/c8ra05686b. eCollection 2018 Aug 20.

Authors

Isao Yamaguchi¹, Yuki Tanaka¹, Aohan Wang¹

Affiliation

¹ Department of Chemistry, Shimane University 1060 Nishikawatsu Matsue 690-8504 Japan iyamaguchi@riko shimane-u.ac.jp.

Abstract

Reaction of N-(2,4-dinitrophenyl)pyridinium chloride (salt(Cl^-)) with sodium dicyanamide (Na(CN)₂N) resulted in anion exchange between Cl^- and (CN)₂N^- to yield a new Zincke salt, salt((CN)₂N^-). Reactions of salt((CN)₂N^-) with piperazine, specifically (R)-(-)- or (S)-(+)-2-methylpiperazine under eco-friendly conditions, such as in aqueous solution, in the absence of a catalyst, and at room temperature, resulted in pyridinium ring opening to yield ionic high-molecular-weight polymers with 5-2,4-dienylideneammonium dicyanamide units or chiral 5-(2-methylpiperazinium)-2,4-dienylideneammonium dicyanamide units, namely, polymer(H;(CN)₂N^-), polymer(R-Me;(CN)₂N^-), and polymer(S-Me;(CN)₂N^-). UV-Vis measurements revealed that the π-conjugation system expanded along the polymer chain due to the orbital interaction between the electrons on the two nitrogen atoms of the piperazinium ring. Circular dichroism (CD) measurements revealed a helical conformation of the main chain in polymer(R-Me;(CN)₂N^-) and polymer(S-Me;(CN)₂N^-). The reaction of polymer(H;(CN)₂N^-) with p-phenylenediamine (PDA) caused recyclization of the 2,4-dienylideneammonium unit and resulted in depolymerization to yield N-(4-aminophenyl)pyridinium dicyanamide. Cyclic voltammetry analysis suggested that the polymers obtained in this study undergo electrochemical oxidation and reduction.