Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined as vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation and reprocessing without depolymerization. We disclose herein the development of functional and high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable networks with high ionic content are obtained by the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer and simultaneous alkylation of the resulting poly(1,2,3-triazole)s with a series of difunctional cross-linking agents. Temperature-induced transalkylation exchanges of C-N bonds between 1,2,3-triazolium cross-links and halide-functionalized dangling chains enable recycling and reprocessing of these highly cross-linked permanent networks. They can also be recycled by depolymerization with specific solvents able to displace the transalkylation equilibrium, and they display a great potential for applications that require solid electrolytes with excellent mechanical performances and facile processing such as supercapacitors, batteries, fuel cells, and separation membranes.
International audience1,2,3-Triazolium-based poly(ionic liquid)s containing a triethylene glycol spacer were synthesized from the polyaddition of an alpha-azide-omega-alkyne monomer by copper-catalyzed azide-allcyne cycloaddition (CuAAC) followed by quaternization reactions with alkyl halides and subsequent anion exchanges with different fluorinated salts. A detailed structure-property relationship for solubility, thermal stability, and ionic conductivity was investigated by means of H-1 NMR spectroscopy, differential scanning calorimetry (DSC), thermogravinietric analysis (TGA), and broadband dielectric spectroscopy (BDS). One of these poly(ionic liquid)s with a methyl substituent and bis(trifluoromethylsulfonyl)imide anion exhibits an ionic conductivity of 2 x 10(-5) S cm(-1) at 30 degrees C, which is on par with the best PILs with side-chain charge carriers reported so far and is much higher than any previously reported ionenes. The straightforward synthesis along with the broad structural design and enhanced properties of this new class of poly(ionic liquid)s offer both fundamental and applicative perspectives
A series of anionic poly(ionic liquid)s
with 1,2,3-triazolium counter
cations are prepared by cation exchange between tailormade 1,3,4-trialkylated-1,2,3-triazolium
iodides and a polystyrene derivative having pendant potassium bis(trifluoromethylsulfonyl)imide
groups. The physical and ion-conducting properties of the resulting
materials are compared to the parent potassium-containing polyelectrolyte
based on 1H NMR, differential scanning calorimetry (DSC),
thermogravimetric analysis (TGA), and broadband dielectric spectroscopy
(BDS) measurements. Substitution of the potassium counter cation by
1,2,3-triazolium charge carriers affords polyelectrolytes with improved
processability (broader solubility and removal of the crystalline
behavior) as well as a substantial increase in anhydrous ionic conductivity.
International audienceA straightforward and expeditious monotopic approach for the preparation of 1,2,3-triazolium-based poly(ionic liquids) (TPILs) is reported. It is based on the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer in the presence of methyl iodide or N-methyl bis[(trifluoromethyl)sulfonyl]imide alkylating agents. Poly(1,2,3-triazole)s generated in bulk or by thermal azide-alkyne cycloaddition (AAC) are quaternized in-situ to afford TPILs composed of 1,3,4- and 1,3,5-trisubstituted 1,2,3-triazolium units. The physical and ion-conducting properties of the prepared samples are compared with the TPILs composed solely of 1,3,4-trisubstituted 1,2,3-triazolium units obtained through a multistep approach involving copper(I)-catalyzed AAC polyaddition, quaternization of the 1,2,3-triazole groups, and anion metathesis. TPILs obtained through the monotopic approach display thermal stabilities and ionic conductivities comparable to their pure regioisomeric analogues
Herein we describe the synthesis and characterization of a neutral heteroleptic iridium complex bearing an unusual 2-pyridyl-6-methylthiazine dioxide ligand (pythdo). X-ray crystallographic analysis reveals that in the complex, the pythdo ligand is twisted and puckered, resulting in very low photoluminescent quantum efficiency. The emission profile is structured. Excited state lifetime measurements along with oxygen quenching studies point to a rare case of dual emission from different excited states whereby the high energy bands possess significant ligand-centered ((3)LC) character while the lower energy bands are predominantly characterized as a mixture of charge transfer ((3)CT) states. A detailed computational analysis corroborates the unusual photophysical behavior.
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