Paramagnetic iron-containing ionic liquid crystals

Abstract

Iron-containing ionic liquid crystals of N,N′-dialkylimidazolium salts ([(CnH2n+1)2IM]3[Fe(CN)6], with n = 12 (1), 14 (2), 16 (3), 18 (4), IM = imidazolium) were prepared and their structures and properties were characterized. Differential scanning calorimetry (DSC), polarizing optical microscopy (POM) as well as powder X-ray diffraction (PXRD) analysis reveal for all compounds thermotropic liquid crystalline behavior. The observed textures point to smectic A and smectic X phases. The crystal structure of the solvate [C12C12IM]3[Fe(CN)6]·2 DMSO (DMSO = dimethylsulfoxide) was examined by single crystal X-ray diffraction analysis which reveals two crystallographically independent [C12C12IM]+ cations with different conformation, U-shape and rod-shape, together with a nearly ideal octahedral [Fe(CN)6]3− anion and two DMSO solvent molecules. The crystal packing is characterized by alternating bilayers of almost linearly arranged imidazolium cations with the U-shaped cations being arranged in a head-to-head fashion and the cations' hydrophobic dodecyl chains being interdigitated. Magnetic measurements for compounds 1–4 show paramagnetic moments, μeff, of ~1.7 μB, which are close to the theoretically expected value for a d5 low-spin Fe3+ spin-only S = 1/2 system (μeffs.o. = 1.73 μB). It was possible to obtain an Fe3+ containing ILC material that combines liquid crystalline behavior over a large mesophase window (from 33 °C to 170 °C) with high magnetic susceptibility by mixing compound 3 with [C16C16IM][FeCl4] (5), which contains the d5 high-spin Fe3+ ion (S = 5/2). All compounds are highly hydrophobic and stable in the atmosphere indicating a great potential of applications as functional materials.