Bent-core V-shaped mesogens consisting of salicylaldimine mesogenic segments: synthesis and characterization of mesomorphic behaviour

Abstract

A series of bent-core V-shaped mesogens consisting of salicylaldimine mesogenic segments have been synthesized and their mesomorphic behaviour characterized. In an attempt to understand structure–property relationships, the lengths of the terminal alkoxy chains have been varied from C₂ to C₁₂, C₁₆ and C₁₈, resulting in 13 new bent-core V-shaped molecules. The thermal behaviour of these new compounds has been investigated by optical microscopy, calorimetry and X-ray diffraction studies. In general the compounds show conventional mesophases similar to those shown by calamitic LCs. The materials exhibit good thermal stability, even though their melting and clearing transition temperatures are high as a result of the presence of intramolecular hydrogen bonding between the H-atom of the hydroxyl group and the N-atom of the imine functionality. The phase appearing in the first member of the series with ethoxy chains is a nematic, while the C₃ to C₆ derivatives exhibit a smectic A phase as well as a nematic phase. The higher homologues, C₇ to C₁₂, C₁₆ and C₁₈, show only the smectic A phase. X-ray studies reveal that the SmA phase has a partially bilayer (interdigitated) structure. Remarkably, in some cases, the smectic A phase supercools well below room temperature. It is apparent from our studies that increasing the length of the alkoxy chains promotes smectic behaviour, in agreement with the general observation made for such bent-core molecules.