1,3,4,5-Tetrasubstituted Poly(1,2,3-triazolium) Obtained through Metal-Free AA plus BB Polyaddition of a Diazide and an Activated Internal Dialkyne

A tetra(ethylene glycol)-based 1,3,4,5-tetrasubstituted poly(1,2,3-triazolium) is synthesized in two steps including: i) the catalyst-free polyaddition of a diazide and an activated internal dialkyne and ii) the N-alkylation of the resulting 1,2,3-triazole groups. In order to provide detailed structure/properties correlations different analogs are also synthesized. First, parent poly(1,2,3-triazole)s are obtained via AA+BB polyaddition using copper(I)-catalyzed alkyne-azide cycloaddition or metal-free thermal alkyne-azide cycloaddition (TAAC). Poly(1,2,3-triazole)s with higher molar masses are obtained in higher yields by TAAC polyaddition. A 1,3,4-trisubstituted poly(1,2,3-triazolium) structural analog obtained by TAAC polyaddition using a terminal activated dialkyne and subsequent N-alkylation of the 1,2,3-triazole groups enables discussing the influence of the methyl group in the C-4 or C-5 position on thermal and ion conducting properties. Obtained polymers are characterized by 1H, 13C, and 19F NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, size exclusion chromatography, and broadband dielectric spectroscopy. The targeted 1,3,4,5-tetrasubstituted poly(1,2,3-triazolium) exhibits a glass transition temperature of -23 degrees C and a direct current ionic conductivity of 2.0 x 10-6 S cm-1 at 30 degrees C under anhydrous conditions. The developed strategy offers opportunities to further tune the electron delocalization of the 1,2,3-triazolium cation and the properties of poly(1,2,3-triazolium)s using this additional substituent as structural handle. A 1,3,4,5-tetrasubstituted poly(1,2,3-triazolium) is synthesized by catalyst-free AA+BB polyaddition of tetraethylene glycol-based diazide and activated internal dialkyne monomers followed by N-alkylation of the 1,2,3-triazole groups using N-methyl bis[(trifluoromethyl)sulfonyl]imide. Structure/properties correlations are discussed comparing structural analogs obtained through copper(I)-catalyzed or thermally activated azide-alkyne 1,3-dipolar cycloaddition step growth polymerizations using terminal or internal activated dialkynes. image