Imidazolium-type anion exchange membranes for improved organic acid transport and permselectivity in electrodialysis

Most commercial anion exchange membranes (AEMs) deploy quaternary ammonium moieties. Alternative cation moieties have been explored in AEMs for fuel cells, but there are no studies focused examining alternative tethered cations in AEMs for ionic separations – such as organic acid anion transport via electrodialysis. H-cell and conductivity experiments demonstrate that tethered benzyl 1-methyl imidazolium groups in polysulfone AEMs enhance lactate conductivity by 49% and improved lactate anion flux by 24x when compared to a quaternary benzyl ammonium polysulfone AEM. An electrodialysis demonstration with the imidazolium-type AEM showed a 2x improvement in lactate anion flux and 20% improvement in permselectivity when benchmarked against the quaternary ammonium AEM. Molecular dynamics and 2D NOESY NMR revealed closer binding of lactate anions to the imidazolium cations when compared to the quaternary ammonium cation. It is posited that this closer binding is responsible to greater flux values observed with imidazolium-type AEM.

Syntheses, crystal structures, and fluorescent properties of three coordination polymers with 5-sulfoisophthalic acid anion and 4-phenylpyridine

Three coordination polymers—{[Ag2(SIP)(4-pp)]·[Ag(4-pp)2]·H2O}n, [Pb4(SIP)2( μ3-OH)2(H2O)2]n, and {[Zn2(SIP)2(4-pp)4][Zn(4-pp)2(H2O)4]·4H2O}n (SIP = 5-sulfoisophthalic acid anion, 4-pp = 4-phenylpyridine)—are constructed under hydrothermal or solvothermal conditions using sodium m-phthalate 5-sulfonate (NaH2SIP) and 4-phenylpyridine as ligands. The structures of the three complexes are determined by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analyses, Fourier-transform infrared analysis, and photoluminescence. The fluorescent properties of the complexes in the solid state are investigated at room temperature, and the results indicate that they all show photoluminescent properties.

Monosulfonated Azo Dyes: A Crystallographic Study of the Molecular Structures of the Free Acid, Anionic and Dianionic Forms

Crystallographic studies of monosulfonated azo dyes have concentrated on the salt forms that contain the azo anion. Here we present a study that compares the structures of these anions with protonated free acid forms and with doubly deprotonated dianion forms. To this end, the new single crystal diffraction structures of 13 systematically related free acid forms of monosulfonated azo dyes are presented, together with three new structures of doubly deprotonated forms and two new structures of Na salt forms of azo anions. No structures of dideprotonated monosulfonated azo dyes have previously been reported and this paper also reports the first crystal structure of an azo dye with a hydronium cation. The geometries of the free acid, anion and dianion forms are compared to literature equivalents. It is shown that protonation of the azo bond gives predictable bond lengthening and shortening, which is of a greater magnitude than similar effects caused by azo-hydrazone tautomerisation, or the smaller again effects caused by the resonance electron donation from O or N based substituents. The dianion containing structures have twisted dianion geometries that can be understood based on the resonance effects of the phenoxide groups and upon the needs to bond to a relatively high number of metal cations.