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It is demonstrated in electro-optic experiments that an external electric field of the order of 10;{5} V/m induces persisting texture transitions in a nematic phase formed by bent-core mesogens. The field-induced metastable state is identified by its optical and electric properties. After the field is switched off, the original and induced states can coexist in domains for about one hour in planar sandwich cells. During this time, the induced domains gradually shrink but they can be stabilized in moderate electric fields. The occurrence of similar domains in homeotropic cells suggests that the transition into a metastable biaxial state is observed. In the field-free planar ground state, the formation of inversion walls is observed inside the metastable domains.

Density functional theory (DFT) calculations and molecular dynamics (MD) simulations on the atomic level were performed on three different substituted banana-shaped compounds derived from 1,3-phenylene bis[4-(4-n-hexyloxyphenyliminomethyl)benzoate] (P-6-O-PIMB). The DFT studies were carried out on the isolated molecules, and in the MD simulations clusters were treated with up to 64 monomers. The effect of polar substituents, such as chlorine and the nitro group, on the central 1,3-phenylene unit of banana-shaped compounds was investigated. In particular, flexibility, polarity, electrostatic potential (ESP) group charge distributions, B-factors, bending angles and molecular lengths were considered. The MD results were analysed by trajectories of significant torsion angles as well as order parameters such as radial atom pair distribution functions g(r), orientational correlation functions g(o), diffusion coefficients (D) and root mean square deviations (RMSD) values. The g(r) and g(o) values show that a certain long range order is generated by the introduction of a NO(2) group in the 2-position of the central 1,3-phenylene ring. In contrast, the chlorination at the 4 and 6 positions of the central 1,3-phenylene unit decreases the long range order tendency by its perturbation effect on the conformations in such molecules. Moreover, g(r) and g(o) values, as well as diffusion coefficients, show that in the NO(2) substituted compound the formation of microphase areas is preferred. Finally, the aggregation effect in such compounds was studied in a systematic way by a comparison of the conformational properties of the isolated molecules and the monomers in the clusters.

The purpose of this paper is the demonstration that bent core nematic phases behave quantitatively and qualitatively very different from ordinary calamitic nematics in their electro-optical characteristics. We present measurements of the elastic properties from the analysis of Brochard-Leger walls that are formed during the splay Fréedericksz transition in sandwich cells. These walls possess an unusually large shape anisotropy as compared to similar structures in calamitic nematics. The wall shapes can be explained when one assumes that the bend elastic constant K(33) is one order of magnitude larger than the twist constant K(22) of the material, supposing that flexoelectricity in the description of the elastic deformations can be neglected. Further we report periodic structures above the splay Fréedericksz transition with a wave vector perpendicular to the director easy axis. They represent either a static instability or an unconventional type of electrically driven convection.

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.

New five-ring bent-core mesogens that possess only ester connecting groups between the aromatic rings and different lateral substituents at the central phenyl ring are presented. The mesophases have been assigned by polarizing microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical measurements. It is shown that the mesophase behaviour depends strongly on the position of the lateral substituents. Compounds, which are derived from 4-cyano-, 4-chloro- and 4,6-dichloro-resorcinol, show polymorphism variants where polar phases (SmAP, SmCP) occur together with nematic and conventional smectic phases, e.g. SmA-SmAP, SmA-SmC(S)P(A)-Col(ob)-SmC(S)P(A), N-SmA-SmCP(A), SmA-SmC-SmCP(A) and SmC-SmCP(A). On the basis of the behaviour of two series of materials, the occurrence of different polar-switching mechanisms could be demonstrated. Apart from the usual mechanism by director rotation around the tilt cone, the polar switching can also take place through collective rotation of the molecules around their long axes, which corresponds to a field-induced switching of the layer chirality. A remarkable finding is the polar switching in the crystalline modification of long-chain, bent-core compounds with a methyl group in 2-position, which is accompanied by a clear change of the optical texture and by a relatively high switching polarization (approx. 600 nC cm(-2)). It was found for selected bent-core compounds that, above the transition temperature of a polar to a non-polar phase, the non-polar phase can be transformed to the polar phase by application of an electric field, which was proved for the transitions isotropic-SmCP(F), SmA-SmCP(F) and isotropic-CrII polar.

Material with the phase sequence SmA-SmAP-SmCP is studied as an example of a system in which the spontaneous electric polarization and the molecular tilt develop independently at the SmA-SmAP and the SmAP-SmCP phase transition, respectively. The temperature dependence of the spontaneous electric polarization clearly shows a strong coupling between the polarization and tilt. The system exhibits also very strong precritical polarization and tilt fluctuations. Experimental observations are explained within the theoretical model.

Langmuir layers of a symmetric bent-core molecule with hydrocarbon end chains and two chlorine atoms substituted on the central phenyl ring of the bent core were characterized by a combination of surface pressure isotherms, Brewster angle microscopy, and surface potential measurements. These layers were found to be optically anisotropic, in contrast to Langmuir layers of similar molecules with different substitutions on the core. After compression, the orientation of the optical axis was essentially uniform over the film. Upon decompression, the film broke into uniform islands or domains. Measuring domain reflectivity while changing the domain orientation allowed the determination of the tilt angle with respect to both domain features and the film normal, as well as the refractive index anisotropy. The tilt angle, near 90 degrees, suggests that the bent-core molecules lie quite flat on the surface.

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.

We demonstrate the homogeneous and permanent reversal of the chirality of a condensed phase by an applied electric field. Tilted chiral smectic layers exhibit a coupled polarization density and molecular orientation fields which reorient about the layer normal as couple of fixed handedness in response to small applied electric fields. Experiments on some bent-core smectics show that above a threshold field the induced rotation can occur instead about the molecular long axis and that, as a result, the handedness of the phase can be flipped. The effect is quantitatively described by a nonequilibrium dissipative model of chiral smectic dynamics with anisotropic rotational viscosities.

Stable free-standing liquid filaments formed by some layered mesophases of bent-core mesogens are unique structures. Some of their physical properties have been analyzed in recent studies, but their microscopic structure and conditions for stability have still been unclear. We explore details of filament shapes and surface profiles of filaments drawn in liquid crystal phases of bent-core mesogens by AFM and SEM measurements, and we present a microscopic structure model. Conclusions on the stabilizing mechanisms are drawn. Qualitative differences in mechanical properties are found for different mesophases, even though the macroscopic appearance of the filaments is very similar.

We found that the optically isotropic (I(M)) mesophase observed recently below the nematic phase of the bent-core liquid crystal 4-chlororesorcinol bis[4-(4-n-dodecyloxybenzoyloxy)benzoate] shows ferroelectric-type switching. Polarizing microscopic, electric current, dielectric, and dynamic light scattering studies lead us to propose that the I(M) phase is composed of interconnected orthoconic racemic smectic (Sm-Ca P(F)) nanodomains with random layer orientations. Near the nematic phase, where the polarization can be saturated by electric fields, the system responds in a fashion analogous to the granular structure of a magnetic spin glass--in particular, we observed that the relaxation back to the nonpoled structure follows a similar, inverse logarithmic rule.

The formation of stable freely suspended filaments is an interesting peculiarity of some liquid crystal phases. So far, little is known about their structure and stability. Similarly to free-standing smectic films, an internal molecular structure of the mesophase stabilizes these macroscopically well-ordered objects with length to diameter ratios of 10(3) and above. In this paper, we report observations of smectic liquid crystal fibers formed by bent-shaped molecules in different mesophases. Our study, employing several experimental techniques, focuses on mechanical and structural aspects of fiber formation such as internal structure, stability, and mechanical and optical properties.

Employing null transmission ellipsometry and depolarized reflected light microscopy, we have studied two smectic phases, Sm-C1 and Sm-C2, of one achiral mesogen. Our results show that Sm-C1 and Sm-C2 are the synclinic Sm-C and anticlinic Sm-C(A) phases, respectively. We find no evidence to support recent claims that the Sm-C1 is chiral and ferroelectric [R. Stannarius et al., Phys. Rev. Lett. 90, 025502 (2003)].

A detailed study of the dynamics of electro-optical response has been carried out over the whole temperature range of the antiferroelectric B2 phase of a compound with bent-core shape molecules, a homolog (n=14) of the series 4-chloro-1,3-phenylene bis[4-(4-n-alkylphenylimino)benzoates]. Two types of stripe domains were observed with opposite handedness and simultaneous clock and anticlock motion of the director in the neighboring domains. The temperature dependence of the interlayer potential has been found from the threshold of the transition from the ground antiferroelectric (AF) state to the field-induced ferroelectric (F) state. The rotational viscosity gamma(phi) has been calculated from the dynamics of the field-induced azimuthal director switching between F-F and AF-F states and free relaxation of the director from F to AF state. The electro-optical response was also observed below the AF-F threshold. The latter was attributed to the soft-mode distortion of the molecular tilt angle in the vicinity of the transition from the B2 phase to the isotropic phase.

We report the experimental results on pure fluorinated bent-shaped mesogens showing very unusual textures and electro-optical behavior. In the view of recent publications such behavior can be explained by triclinic symmetry of the mesophase (Sm-C(G)) formed by these compounds. Based on the results of the x-ray diffraction and electro-optical investigations, we give evidence for the Sm-C(G) -->Sm-CP polymorphism.

A tilted smectic phase of a new achiral banana-shaped mesogen is presented. It possesses liquidlike order within the layers and appears with a fan-shaped texture. At sufficiently high electric fields, this texture can be transformed into a texture that displays a complete extinction between crossed polarizers and it forms randomly distributed chiral domains. Above a threshold these domains can be reversibly switched into a state of opposite handedness.

We report electro-optic experiments in liquid crystalline freestanding films of achiral hockey stick shaped mesogens with a straight aromatic core. The material forms two smectic mesophases. In the higher temperature phase, a spontaneous polarization exists in the smectic layer plane and the films show polar switching in electric fields. It is the first example of a ferroelectric phase formed by nearly rodlike achiral mesogens. Mirror symmetry of the phase is spontaneously broken. We propose a molecular configuration similar to a synclinic ferroelectric (C(S)P(F)) high temperature phase and an anticlinic, probably antiferroelectric (C(A)P(A)) low temperature phase.

We report the electro-optic investigation of a liquid crystalline free standing film formed by bent-core (banana-shaped) mesogens. The ground state of the B2 phase in the films is chiral and antiferroelectric, although the mesogenic molecules themselves lack chirality. The films can be switched in lateral electric fields. In the antiferroelectric ground state, the external electric field in the film plane couples to a small residual spontaneous polarization which we attribute to the incomplete compensation of polarizations of neighboring smectic layers, due to a nonzero twist normal to the layers. We derive viscoelastic parameters from the uniform switching dynamics and the structure of domain walls. Dynamic patterns in rotating fields are observed and analyzed.

We have studied one banana-shaped compound using null-transmission ellipsometry. By studying free-standing films of various thicknesses we confirm that this compound exhibits the Sm-A phase. This is the first banana-shaped compound with a relatively small bend angle (approximately 140 degrees) in which a uniaxial phase has been observed. At the lower temperature end of the Sm-A phase we observe unusual ordering at the surface of the film.

We report unambiguous experimental evidence for an achiral orthogonal biaxial smectic-A phase which exhibits antiferroelectric switching behavior. The evidence is based on x-ray-diffraction measurements, texture observation, and the results of dielectric and electro-optical measurements.

Null-transmission ellipsometry has been performed on free-standing films of one compound in the liquid crystal B2 phase. We have studied films of thickness from 1 to 121 layers. One of the compounds used has an unusually wide 59 K window for the B2 phase. The tilt angle was investigated as a function of temperature and found to be constant over this temperature range to within our resolution of 1 degrees. The one-layer films studied exhibit the same structure as the thicker films, and have helped us to refine the optical model for the B2 phase. For thin films we find that modeling a single smectic layer as two uniaxial layers is a better description of the data than a single biaxial layer, but that for thick films the model used does not effect the simulated result appreciably. Preliminary results also find that the surface layers are less tilted than the interior layers, in contrast to rodlike liquid crystals, which show an enhanced surface tilt.

Lysolipid analogues were synthetized and tested for haemolytic activity. Initial substances were long-chain 2-methylalkanols, as well as 2-hexadecylpropane-1,3-diol. The latter compound was prepared starting with hexadecylmalonic acid diester. Among the compounds synthetized, there were also 1-acetoxy-2-hexadecylpropan-3-ol-phosphocholine and acidic-reacting lysolipid analogues.

Physiologically stable structure analogues of the platelet-activating factor (PAF-acether), the acetyl group of which had been substituted by short-chain alkyl rests, had been synthesized and been tested with regard to their biological activity against thrombocytes. Five differently substituted 2-alkylmalonic acid esters with methyl rest up to n-pentyl rest had been applied the basic products. The n-propyl compound exhibits the most intense biological activity, which is, however, essentially reduced against the PAF-acether. With conditions of the examination, all the other derivatives possess a more decreased activity.