Synthesis and properties of oxadiazole based V-shaped, shape persistent nematogens.

A series of biaxial V-shaped, shape-persistent molecules has been synthesised by stepwise coupling of phenylene ethynylene arms to an oxadiazole bending unit. Studies of their thermotropic nematic phases point to phase biaxiality.

Layer frustration, polar order and chirality in liquid crystalline phases of silyl-terminated achiral bent-core molecules.

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.

DFT and MD studies on the influence of the orientation of ester linkage groups in banana-shaped mesogens.

The influence of the direction of ester linkage groups on the structural and electronic properties of five-ring banana-shaped molecules with a central 1,3-phenylene unit has been investigated including hexyloxy and dodecyloxy terminal chains. DFT studies on the B3LYP/6-31G(d) level were performed on the conformational behaviour of the ten isomers in a systematic way. The one- and two-fold potential energy scans show that the flexibility of the wings significantly depends on the orientation of the carboxyl linkage groups. Moreover, the different directions of the carboxyl groups between the aromatic rings cause remarkable changes on the dipole moment and its components of the molecules. These findings are supported by investigations on the global charge pattern of the molecules calculated from electrostatic potential group charges. The bending angle alpha obtained from a simple model for the five-ring bent-core molecules is a characteristic structural parameter which can be correlated with experimental findings. Calculations on the bent-core molecules in an external electric dipole field related to the direction of their polar axis show remarkable effects with respect to the flexibility and polarity of the isomers. First molecular dynamics simulations on the banana-shaped molecules were carried out within the AMBER 7 package. The trajectories of relevant structural parameters support the findings of the DFT studies. The results concerning the structure and polarity revealed from the DFT and MD calculations of the ten isomers can be correlated with data from dielectric measurements and mesophase properties.

Mesogenic dimers composed of a calamitic and a bent-core mesogenic unit.

Three mesogenic dimers have been synthesized in which a five-ring bent-core moiety is connected with different calamitic units flexible spacers. The mesophase behavior of the dimers have been investigated by polarizing microscopy, differential scanning calorimetry, X-ray diffraction on oriented samples and by dielectric and electro-optical measurements. We found that two dimers exhibit a dimorphism columnar-nematic whereas the third one forms a columnar phase only. On the basis of the X-ray data a possible structure model of one of the columnar phases is proposed. The nematic phase exhibits unusual properties. A smectic-like texture can be induced by applying an electric field, which is unknown for nematic phases formed by rod-like mesogens.

Dipolar interactions in liquids and linear dielectric relaxation spectroscopy.

Linear dielectric relaxation studies performed on two isotropic liquids composed of the molecules of the same moment of inertia and a quite different polarity: C10H21-O-Ph-COO-Ph-CN (the dipole moment of about 5 D) and C10H21-O-Ph-OOC-Ph-CN (2.5 D) showed that, at given temperature, the relaxation times corresponding to the rotation around the short axis of the two kinds of molecules coincide to each other, regardless the polarity of the molecules and their abilities to accomplish dipolar aggregation. The studies allow one to estimate the lifetime of the intermolecular aggregates due to the dipolar interactions in liquids as no longer than 0.1 ns.

Static and dynamic dielectric behavior of mesogenic compounds of different polarity in the vicinity of the isotropic to nematic phase transition.

Mesogenic compounds belonging to the two well-known -cyanophenyl, and -isothiocyanatophenyl homologous series, which distinctly differ in the molecular polarity (-C identical with N, 5D; -N=C=S, 2.5D), show an essential difference in the pretransitional dielectric behavior in the vicinity of the isotropic to nematic (I-N) phase transition. Taking into account the results presented in Phys. Rev. E 67, 041705 (2003), the features of the I-N transition observed for the less polar mesogens are characteristic for the first order phase transition, whereas in the case of the strongly polar ones, the I-N transition is undoubtedly close to the second order.

Evidence for a new ferroelectric switching liquid crystalline phase formed by a carbosilane based dendrimer with banana-shaped mesogenic units.

The first carbosilane dendrimer with peripheral bent-core mesogenic units is reported. This material forms a liquid crystalline phase which is stable over a wide temperature range and forms an LC glass on cooling. Polarizing microscopy, X-ray diffraction, and dielectric and electrooptic investigations reveal the presence of a novel liquid crystalline phase, in which the molecules are tilted and adapt a polar order within the layers, but without long-range correlation between the layers. By applying external electric fields, switching into a ferroelectric organization can be achieved. Once formed the ferroelectric states are stable and can be switched between the different polarization states.