A novel class of bent-core molecules with oligo(siloxane) or carbosilane units at both ends was synthesized and the self-organization of these molecules was investigated by polarizing microscopy, DSC, X-ray scattering, dielectric and electrooptical methods. Depending on the size of the silicon-containing segments, smectic and columnar liquid crystalline phases are formed. Most smectic phases are low birefringent and composed of macroscopic domains of opposite handedness (dark conglomerate phases). The switching process in these smectic phases is surface stabilized ferroelectric and, depending on the conditions, two distinct slow relaxation processes to nonpolar structures were observed. It is proposed that the smectic phases are built up by chiral and polar SmCsPF layer stacks which are separated by anticlinic interfaces. If the size of these layer stacks is sufficiently large a coupling to the substrate surfaces takes place and ferroelectric switching is observed. It is also suggested that the sponge-like layer distortion, occurring in the low birefringent mesophases, is due to an escape from the local polar order within these SmCsPF layer stacks. For compounds with larger silylated units a steric frustration arises, which leads to layer modulation (columnar ribbon phases) and this is associated with a transition from ferroelectric to antiferroelectric switching. All compounds show a switching of the molecules around the long axis which reverses the layer chirality.

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Novel bent-core molecules based on phenyl benzoate rigid cores and heptamethyltrisiloxane units at one or at both ends of the aliphatic side chains were synthesized and investigated by polarized light microscopy, differential scanning calorimetry, X-ray diffraction and electrooptical methods and the effect of the direction of the carboxyl groups on the mesomorphic self assembly was investigated. A series of distinct liquid crystalline phases was found, among them ferroelectric and antiferroelectric switching and also non-switchable smectic, undulated smectic (USmC) and modulated smectic phases (columnar phases, Col ob ). All polar phases show field-induced inversion of chirality at least in a certain temperature range. Moreover, two non-polar and uniaxial smectic phases were observed, one with a hollow cone-like orientational director distribution (SmC R ) and the other one with a maximum of the director distribution at zero tilt (SmA). These two phases were discussed in relation to the distinct models of de Vries type smectic phases.

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