1,3,4,5-Tetrasubstituted Poly(1,2,3-triazolium) Obtained through Metal-Free AA+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 °C and a direct current ionic conductivity of 2.0 × 10-6 S cm-1 at 30 °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.

UV-Patterning of Ion Conducting Negative Tone Photoresists Using Azide-Functionalized Poly(Ionic Liquid)s.

The patterning of solid electrolytes that builds upon traditional fabrication of semiconductors is described. An azide-functionalized poly(1,2,3-triazolium ionic liquid) is used as an ion conducting negative tone photoresist. After UV-irradiation through an optical mask, micron-scaled, patterned, solid polyelectrolyte layers with controlled sizes and shapes are obtained. Furthermore, alkylation of poly(1,2,3-triazole)s can be generalized to the synthesis of poly(ionic liquid)s with a tunable amount of pendant functionalities.

RAFT polymerization of bio-based 1-vinyl-4-dianhydrohexitol-1,2,3-triazole stereoisomers obtained via click chemistry.

Four 1-vinyl-4-dianhydrohexitol-1,2,3-triazole stereoisomers are prepared from isomannide, isoidide, and isosorbide using an alkylation/CuAAC-ligation/elimination three-step strategy. After characterization of the monomers by NMR, differential scanning calorimetry (DSC), and high-resolution mass spectrometry (HRMS), the corresponding stereocontrolled poly(1-vinyl-4-dianhydrohexitol-1,2,3-triazole)s are obtained by RAFT polymerization using a xanthate chain transfer agent. A systematic investigation of the structure-properties relationship of both the monomers and polymers highlights the significant impact of the dianhydrohexitols stereochemistry on their physical properties (1H and 13C NMR chemical shifts, physical state, Tg, thermal stability and solubility). A particularly original and unexpected behavior is highlighted since the two different isosorbide-based poly(1-vinyl-4-dianhydrohexitol-1,2,3-triazole) stereoisomers exhibit contrasting solubility in water.

Hairy carbon nanotube@nano-Pd heterostructures: design, characterization, and application in Suzuki C-C coupling reaction.

Poly(glycidyl methacrylate), PGMA, was prepared via ATRP in bulk solution, and its epoxy groups were further acid-hydrolyzed in order to obtain a polymer with glycerol moieties (noted POH). The POH chain end C-Br bonds were subjected to a nucleophilic attack by NaN(3), resulting in azide-terminated POH (POH-N(3)). The CNTs were modified by in-situ-generated alkynylated diazonium cations from the para-alkynylated aniline of the formulas H(2)N-C(6)H(4)-C≡C-H, yielding CNT-C(6)H(4)-C≡C-H nanotubes. The azide-functionalized polymer POH-N(3) was clicked to the alkynyl-modified CNTs giving CNT@POH hybrids, which were further subjected to an oxidation resulting in carboxylated polymer-modified CNTs (noted CNT@PCOOH). The as-designed hairy CNTs served as efficient platforms for the in-situ synthesis and massive loading of 3 nm sized palladium nanoparticles (NPs). The CNT@PCOOH@Pd heterostructures prepared so far exhibited an efficient catalytic effect in the C-C Suzuki coupling reaction and were regenerated up to four times without any significant loss of catalytic activity.