In ionic liquid crystals (ILCs) tilted mesophases such as SmC required for electro-optic devices are quite rare. We report a design concept that induced the SmC phase and enabled de Vries-like behaviour in ILCs. For this purpose, we synthesized and characterized a library of ILC derivatives ImR(On,Ym)X which consist of a rigid central fluorenone core containing an alkoxy or thioether side chain and connected via a flexible spacer to an imidazolium head group. The mesomorphic properties were studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (XRD). Temperature-dependent measurements of smectic layer spacing d by small-angle X-ray scattering (SAXS) and of optical tilt angles by POM demonstrate that ILCs ImR(On,Ym)X undergo SmA-SmC phase transitions with maximum layer contraction values between 0.4% and 2.1%. The lowest reduction factor R of 0.2 at the reduced temperature T - T AC = -10 K was calculated for Im(O12,S14)Br. Electron density calculations indicated a bilayer structure. Furthermore, temperature dependent emission studies show that self-assembling has a strong influence on the emission intensity of these ILCs.
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