| Autor: |
Lozančić, Ana, Burazer, Sanja, Renka, Sanja, Molčanov, Krešimir, Molčanov, Lidija, Jurić, Marijana |
| Předmět: |
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| Zdroj: |
CrystEngComm; 4/7/2024, Vol. 26 Issue 13, p1892-1901, 10p |
| Abstrakt: |
The proton conduction behaviour of novel oxalate-based compounds of iron(III) of different nuclearity with various ammonium components, (NH4)2[Fe(H2O)Cl3(C2O4)]·H2O (1), {[NH(CH3)2(C2H5)][FeCl2(C2O4)]·H2O}n (2) and {[N(CH3)(C2H5)3][FeCl2(C2O4)]}n (3), was investigated by impedance spectroscopy in addition to characterization by single-crystal and powder X-ray diffraction and infrared spectroscopy. The discrete mononuclear compound 1 exhibits a very high proton conductivity of 2.17 × 10−3 (Ω cm)−1 at 25 °C and 74% relative humidity (RH), with σDC increased by nearly seven orders of magnitude. The three-dimensional (3D) hydrogen-bonding network of NH4+ cations and water molecules (crystal and coordinated) as hydrogen-bond donors and the bidentate oxalate ligand and chloride ions of the anionic moiety [Fe(H2O)Cl3(C2O4)]2− as hydrogen-bond acceptors plays a crucial role in proton transport; the density of the formed hydrogen-bonds positively impacts the mobility of protons in the nonporous structure of 1. The one-dimensional (1D) compounds 2 and 3, both containing infinite anionic zig-zag chains [FeCl2(C2O4)]nn− and cations (CH3)2(C2H5)NH+ (2) or (CH3)(C2H5)3N+ (3), showed an increase in conductivity of six and five orders of magnitude, reaching values of 2.00 × 10−4 (Ω cm)−1 and 9.17 × 10−6 (Ω cm)−1, respectively, at 25 °C and 93% RH. Compared to compound 3, compound 2 has hydrogen-bonded protonated (CH3)2(C2H5)NH+ cations that exhibit greater hydrophilicity, which is closely related to the affinity for water molecules that significantly affect proton transport and conductivity. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
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