Synthesis and chemical properties of conjugated polymers with bis(trifluoromethanesulfonyl)imide and bis(nonafluorobutanesulfonyl)imide anions. (October 2019)

• Record Type: Journal Article
• Authors: Yamaguchi, Isao; Nagase, Gintaro; Wang, Aohan
• Is Part Of: European polymer journal. Volume 119(2019)
• Page Start: 359
• Page End: 366
• Publication Date: 2019-10
• Subjects: Conjugated polymer -- Bis(trifluoromethanesulfonyl)imide -- Bis(nonafluorobutanesulfonyl)imide -- Piperazinium ring -- Through space interaction; Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; Polymerization; Polymers; Periodicals; Electronic journals; 547.705
• DOI: 10.1016/j.eurpolymj.2019.08.006
• Languages: English
• ISSNs: 0014-3057

Abstract

Graphical abstract: Highlights: New Zincke salts with bis(perfluoroalkanesulfonyl)imide anions were obtained. π-Conjugated polymers were synthesized by the reactions of the salts with piperazines. The conjugated polymers were electrochemically active and ion conductive. Abstract: The reaction of N -(2, 4-dinitrophenyl)pyridinium chloride (salt(Cl − ) ) with lithium bis(trifluoromethanesulfonyl)imide (TFSI − LI + ) and lithium bis(nonafluorobutanesulfonyl)imide (NFSI − LI + ) resulted in the anion exchange between Cl − and TFSI − and Cl − and NFSI − that yielded new Zincke salts, namelysalt(TFSI − ) andsalt(NFSI − ), respectively. The reaction ofsalt(TFSI − ) with piperazine, ( R )-(–)- or ( S )-(+)-2-methylpiperazines in methanol without the use of a catalyst resulted in the opening of pyridinium ring to yield ionic polymers with 5-piperazinium-2, 4-dienylideneammonium bis(trifluoromethanesulfonyl)imide or 5-(2-methylpiperazinium)-2, 4-dienylideneammonium bis(trifluoromethanesulfonyl)imide units, namelypolymer(H;TFSI − ), polymer( R -Me;TFSI − ), andpolymer( S -Me;TFSI − ), respectively. The reaction ofsalt(NFSI − ) with piperazine yieldedpolymer(H;NFSI − ) having a 5-piperazinium-2, 4-dienylideneammonium bis(trifluoromethanesulfonyl)imide unit. Model compounds with TFSI − or NFSI − were synthesized to compare their structures and chemical propeties with those of the corresponding polymers. 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 or 2-methylpiperazinium rings. Cyclic voltammetry analysis suggested that the polymers obtained in this study received electrochemical oxidation and reduction.