Lozančić, Ana; Burazer, Sanja; Renka, Sanja; Molčanov, Krešimir; Molčanov, Lidija; Jurić, Marijana (2024) Proton transport in oxalate compounds of iron(iii) containing (alkyl)ammonium cations: the influence of the density of hydrogen bonds on conductivity. CrystEngComm, 26 (13). pp. 1892-1901. ISSN 1466-8033
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Abstract
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.
| Item Type: | Article | ||||||||
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| Uncontrolled Keywords: | proton conductivity; oxalate-based compounds | ||||||||
| Subjects: | NATURAL SCIENCES > Chemistry | ||||||||
| Divisions: | Division of Materials Chemistry Division of Materials Physics Division of Physical Chemistry |
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| Depositing User: | Diana Mikoč Radešić | ||||||||
| Date Deposited: | 01 Aug 2024 08:22 | ||||||||
| URI: | http://fulir.irb.hr/id/eprint/8989 | ||||||||
| DOI: | 10.1039/d3ce01267k |
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