Tyrosine-Based Ionic Liquid Crystals: Switching from a Smectic A to a Columnar Mesophase by Exchange of the Spherical...

Synthetic strategies were developed to prepare l-tyrosine-based ionic liquid crystals with structural variations at the carboxylic and phenolic OH groups as well as the amino functionality. Salt metathesis additionally led to counterion variation. The liquid-crystalline properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (WAXS, SAXS). The symmetrical ILC chlorides bearing the same alkyl chain at both the ester and ether but either an acyclic or cyclic guanidinium group displayed enantiotropic SmA₂ mesophases with phase widths of 31-88 K irrespective of the head group. It was particularly the replacement of chloride in the acyclic guanidinium ILC by hexafluorophosphate that induced a phase change from SmA₂ to Col_r . This phase change was attributed to a higher curvature of the interface due to the larger anion, which increased the effective head group cross-sectional area of the amphiphilic ILC. The unsymmetrical acyclic guanidinium chlorides, bearing a constant C₁₄ ester and variable alkyl chains on the phenolic position, formed enantiotropic SmA₂ phases. The derivative with the largest difference in chain lengths, however, displayed a Col_r phase, resulting from discoid aggregates of the cone-shaped guanidinium chloride. The results are discussed in terms of the packing parameters, which indicate that the phase behaviour of the thermotropic tyrosine-based ILCs shows analogies to those of lyotropic liquid crystals.