RESUMO
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.
RESUMO
A 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.
Assuntos
Líquidos Iônicos/síntese química , Polímeros/síntese química , Triazóis/química , Alquilantes/química , Catálise , Hidrocarbonetos Iodados/química , Líquidos Iônicos/química , Íons/química , Modelos Químicos , Estrutura Molecular , Polímeros/química , Espectroscopia de Prótons por Ressonância Magnética , Solventes , Estereoisomerismo , Temperatura , Fatores de TempoRESUMO
The design and syntheses of four self-complementary oligomers that contain an underlying AADD hydrogen bond sequence are presented, and their self-association was examined in the solution and solid state. The molecular recognition between the two strands is highly sensitive to substitutions of their component heterocycles. Substitution with electron-donating and -withdrawing groups and the influence of preorganization has a large effect on the overall stabilities of the complexes studied. In particular, a wide range (>10(5) M(-1)) of stabilities with respect to substitutions at various positions in the AADD oligomers was demonstrated. In the most extreme case, the dimerization constant measured (K(dimer) ≥4.5×10(7) M(-1)) is comparable to the most stable homodimers of neutral AADD arrays reported to date.
RESUMO
Two series of DDD and AAA hydrogen-bond arrays were synthesized that form triply-hydrogen-bonded double-helical complexes when combined in CDCl(3) solution. Derivatization of the DDD arrays with electron-withdrawing groups increases the complex association constants by up to a factor of 30 in those arrays examined. Derivatization of the AAA arrays with electron donating substituents reveals a similar magnitude effect on the complex stabilities. The effect of substitution on both types of arrays are modeled quite satisfactorily (R(2) > 0.96 in all cases) as free energy relationships with respect to the sums of their Hammett substituent constants. In all, the complex stabilities can be manipulated over more than three orders of magnitude (>20 kJ mol(-1)) using this type of modification.
RESUMO
In the title compound, C(5)H(8)N(3) (+)·C(24)H(20)B(-)·C(20)H(18)N(6), the 1,2-bis-(5,7-dimethyl-1,8-naphthyridin-2-yl)diazene mol-ecule is essentially planar (r.m.s. deviation = 0.0045â Å) and aligned in nearly coplanar manner with the 2,6-diamino-pyridinium ion, making a dihedral angle of 5.19â (5)°. The diamino-pyridine mol-ecule is protonated on the central pyridine N atom and the B atom bears the counter-charge. The amine groups of the diamino pyridinium cation form intra-molecular N-Hâ¯N hydrogen bonds, resulting in linear and bent inter-actions with the naphthyridine ring system.
RESUMO
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.
RESUMO
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.
RESUMO
Molecular strands incorporating three hydrogen bond donor (D) or acceptor (A) heterocycles form highly stable double helical complexes through a complementary AAA-DDD array structure.