Optical activity produced by layer chirality in bent-core liquid crystals

Large optical activity has recently been observed in chiral smectic liquid crystalline phases formed from achiral bent-core molecules. The origin of the optical activity remains unclear and has been attributed to both a helical superstructure and the layer chirality produced by simultaneous tilt and polar ordering of bent-core mesogens in the B2 phase. Here, we directly demonstrate that layer chirality produces optical activity in the well ordered SmC(A)P(A) subphase.     

Ferroelectric smectic phase formed by achiral straight core mesogens

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.     

Field-induced phase transitions and reversible field-induced inversion of chirality in tilted smectic phases of bent-core mesogens

Three homologous achiral five-ring bent-core mesogens are presented where 4-chlororesorcinol is the central core and the aromatic rings are linked by ester groups. These compounds form smectic phases with a tilted arrangement of the molecules (tilt angle ≈ 45^°). On cooling the isotropic liquid this phase adopts a fan-like texture which shows for two homologues at relatively high electric fields ( 25-35V μm^-1) an antiferroelectric electro-optical response based on the collective rotation of the molecules around their long axes. At lower temperature the application of a sufficiently high electric field leads to a continuous transition into a non-birefringent texture which exhibits randomly distributed domains of opposite handedness. These domains can be reversibly switched into a state of opposite chirality by reversal of the field polarity. This switching is bistable and shows a current response typical for a ferroelectric ground state. The possible mechanism of the field-induced phase transition, of the ferroelectric switching and of the field-induced inversion of the chirality is discussed on the base of XRD, ¹³C- and ¹H-NMR investigations, dielectric and electro-optical measurements.     

Symmetries and induced effects in bilayer and multilayer antiferroelectric and ferrielectric liquid crystal phases

The stable antiferroelectric and ferrielectric smectic phases which may arise below a chiral SmA* phase are investigated theoretically. The symmetry and physical properties of the bilayer and multilayer configurations are worked out. Antiferroelectric and ferrielectric bilayer and multilayer configurations, possessing an induced spontaneous ferroelectric polarization component perpendicular to the smectic layers, are shown to take place, as the result of a nonlinear piezoelectric effect. These states of low polar symmetries occur when the angle between the inlayer projections of the dipoles and the director of the molecules is different from 90 degrees.     

Ferrielectric smectic phase with a layer-by-layer change of the two-component order parameter

One of the most remarkable properties of smectics is the wide variety of possible equilibrium structures. In this paper, based on the Landau theory of the phase transitions, the transitions between ferroelectric and antiferroelectric phases and the structure formed by smectic layers with different azimuthal and polar orientations of the molecules were calculated. This unique structure has been predicted [P.V. Dolganov et al., JETP Lett. 76, 498 (2002)] using the minimization of the free energy with respect to the phase and modulus of the two-component order parameter, but never before detected. Recently, a nonresonant Bragg reflection, consistent with the predictions of the model, was found [P. Fernandes et al., Eur. Phys. J. E 20, 81 (2006)] in the ferrielectric smectic C* _FI1(SmC* _FI1) phase. In the three-layer ferrielectric structure with a macroscopic helical pitch, the modulus of the order parameter is larger in anticlinic-like layers and smaller in layers with mixed ordering. The values of the interlayer interactions were determined for smectic liquid-crystalline materials forming different polar structures. The text was submitted by the authors in English.     

Macroscopic properties of smectic liquid crystals

We discuss the macroscopic behavior of smectic C_G liquid crystals. Smectic C_G is the most general tilted smectic phase that is fluid in the layers. It is characterized by global C₁ symmetry. Consequently, it is ferroelectric, pyroelectric and piezoelectric, opening up a number of possible applications for such a phase. As smectic C_G-phase has a macroscopic hand due to its structure, it is a natural candidate to explain the recent experimental observations of left and right-handed helices in a system composed of achiral molecules. We also discuss critically to what extent smectic C_G could be important for liquid crystalline phases formed by banana-shaped molecules. Phase transitions involving a smectic C_G phase and defects of its in-plane director are briefly discussed. Received: 25 March 1998 / Revised: 15 June 1998 / Accepted: 15 July 1998     

Induced anticlinic ordering and nanophase segregation of bow-shaped molecules in a smectic solvent

Recent experiments indicate that doping low concentrations of bent-core molecules into calamitic smectic solvents can induce anticlinic and biaxial smectic phases. We have carried out Monte Carlo simulations of mixtures of rodlike molecules (hard spherocylinders with length/breadth ratio L(rod)/D = 5) and bow-shaped molecules (hard spherocylinder dimers with length/breadth ratio L(ban)/D = 5 or 2.5 and opening angle psi). We find that a low concentration ( 3%) of L(ban)/D = 5 dimers induces anticlinic ( SmC(A)) ordering in an untilted smectic ( SmA) phase for 100 < or = psi < 150. For L(ban)/D = 2.5, no tilted phases are induced. However, with decreasing psi we observe a sharp transition from intralamellar nanophase segregation (bow-shaped molecules segregated within smectic layers) to interlamellar nanophase segregation (bow-shaped molecules concentrated between smectic layers) near psi = 130.     

Phase transitions in ferroelectric liquid crystals

Molecular chirality plays an important role in the science of liquid crystals, leading to cholesteric liquid crystal, blue phases, ferroelectric and antiferroelectric smectic phases and twist grain boundary phases. In all of these mesogens, chirality is an intrinsic property built into the chemical structure of mesogenic molecules. The study of ferroelectric liquid crystals has seen substantial experimental strides. In theoretical aspects, there has been relatively little basic work on this fascinating class of material. This review will try to present a comprehensive overview of the current status of the phase transitions in ferroelectric smectic liquid crystals. The article begins with a brief introduction about the symmetry and structure of ferroelectric mesophases. An attempt is made to identify a range of problems and related questions associated with the study of phase transitions. In the remaining parts of the article the important experimental and theoretical developments are summarized. Finally, some of the future directions have been identified.     

Phase transitions in nanocomposites of hydrogen-bonded dimeric liquid crystals with mesogenic and non-mesogenic components

Microtextural polarization, phase transitions, and electro-optical effects are studied in a series of nanocomposites, grown by mixing alkyloxybenzoic acids (nOBAs), displaying hydrogen-bonded dimeric liquid crystal (LC) state, with non-mesogens (single-walled carbon nanotubes (SWCNTs), perfluorooctanoic acid) or mesogens (bent-core LC compound D14F3). Each of the studied nanocomposites, in which the nOBA serves as a matrix, forms complexes with bent-shaped dimeric, caused by the interaction between the dopant structural units and the dimer rings. This feature, coordinated with the surface anchoring, bulk and electrical effects, leads to drastic reduction of the LC system symmetry. As a result, transitions from achiral (characteristic for the pristine nOBA) to chiral states (including ferroelectric smectic C with C₂ symmetry and ferroelectric smectic C_G with the lowest C₁ triclinic one) take place. The functionalization of the SWCNTs causes drastic increase of the ferroelectricity.     

Isotropic to ferroelectric and antiferroelectric liquid crystals phase transitions

This review is an attempt towards a unified picture of the direct transitions from the isotropic liquid to ferroelectric and antiferroelectric liquid crystalline phases formed by rod-like and bent-core molecules. The Landau–Ginzburg theories of the phase transitions between the isotropic liquid to ferroelectric and antiferroelectric liquid crystalline phases in compounds composed of chiral rod-like molecules and achiral bent-core molecules are presented. This includes a discussion of the nature of the order parameters and the nature of the various types of phase transitions. The various predictions are compared with the available experimental results.     

Smectic polymorphism of 4-decyloxybenzylidene- 4′-alkyloxyanilines and their mixtures with polar standards of mesophases

This article describes liquid crystalline properties of the homologous series of 4-decyloxybenzylidene-4′-alkyloxyanilines. Based on the polarization microscopy (POM and TOA methods) and the calorimetric (DSC) measurements a rich polymorphism has been detected. Investigated compounds exhibit nematic, smectic A, smectic C, smectic B, smectic I and G (smectic G) mesophases with their characteristic configurations. The presence of these mesophases was confirmed by the miscibility method, using 4-heptyloxybenxylidene-4′-pentylaniline as a mesophase reference. Nine other smectic standards with different polarity have been applied in order to investigate their influence on the mesophase stability.     

On some liquid crystalline phases exhibited by compounds made of bent-core molecules and their mixtures with rod-like molecules

In most homologous series of compounds made of bent-core (BC) molecules, the B₂ B₁ and B₆ phases occur as the chain length decreases. We have studied binary mixtures of the compound 1,3-phenylene bis[4-(3-methylbenzoyloxy)]4-n-dodecylbiphenyl 4’-carboxylate (BC12) which exhibits the B₂ phase with the compound 4-biphenylyl 4’-n-undecyloxybenzoate (BO11) made of rod-like (R) molecules. We find the above sequence of occurrence of the B phases with increasing concentration of BOH. In this paper we describe the physical origin for the formation of these phases in both pure compounds and in the mixtures. We have also found the occurrence of the biaxial smectic A phase when the BO11 concentration is increased to 87–95.5 mol%. We also report on another binary system composed of BC12 and 4-n-octyloxy 4’- cyanobiphenyl (8OCB) made of R molecules. This system exhibits the biaxial smectic A phase down to 30°C. Using polarized infrared spectroscopy we find that the mutual orientation of the R and BC molecules in the SmA_db liquid crystal is such that the arrow axes of the BC molecules are along the layer normal of the partial bilayer smectic structure formed by the rods. We also describe unusual growth patterns obtained when the nematic phase transforms to the SmA_db phase in a mixture with 24 mol% of BC12.     

基于香蕉形液晶分子自组装的纳米螺旋丝有机凝胶及其流变特性

在香蕉形液晶分子B4相态中,非手性香蕉形液晶分子自组装形成层状结构,分子在层内倾斜,形成层手性和自发极化,并且造成层内不匹配,最终形成纳米螺旋丝.本文设计了NOBOW/十六烷混合体系,在高温时,香蕉形液晶分子溶解于十六烷,在低温时,香蕉形液晶分子自组装形成纳米螺旋丝,并最终形成三维网络,变成有机凝胶.为深入理解纳米螺旋丝有机凝胶的特性,拓展其在软物质领域的应用,本文通过流变实验对该有机凝胶的黏弹性质进行了系统研究.实验表明纳米螺旋丝有机凝胶与传统凝胶不同,纳米螺旋丝有机凝胶可以随温度变化形成凝胶-流体的可逆变化,并且通过测量NOBOW/十六烷混合体系在不同液晶分子浓度、温度、应变大小和应变速率下的流变特征,揭示了该有机凝胶的流变特性与纳米螺旋丝的性质密切相关.     

Sequence of four orthogonal smectic phases in an achiral bent-core liquid crystal: evidence for the SmAP(α) phase

The mesomorphic properties of an achiral bent-core liquid crystal derived from 4-cyanoresorcinol are studied by polarizing optical microscopy, x-ray diffraction, and second harmonic electro-optic response. It shows a novel sequence of four nontilted or orthogonal smectic phases on cooling: SmA-SmAP(R)-SmAP(X)-SmAP(A). Here SmAP(X) is the new orthogonal polar uniaxial smectic phase. The electric-field-induced transformations in the SmAP(X) phase give rise to two biaxial states separated by a uniaxial one. The second harmonic electro-optic response in this phase is interpreted in terms of the polar interaction with the electric field. A comparison of the experimental results with the next-nearest-neighbor model for the structure of the SmAP(X) phase shows it to be an SmAP(α) phase.     

Banana-shaped 1,2,4-oxadiazoles

3,5-Disubstituted 1,2,4-oxadiazoles are a new type of liquid crystalline (LC) compounds with asymmetrical five-membered heterocycle as a central unit. They have a bent shape and are very convenient model-compounds for studying the dependence of the LC properties on the molecular design. We have also synthesized and investigated ‘banana-shaped’ 1,2,4-oxadiazoles using the ester groups as the linkage units. The new compounds exhibit spontaneous polarization in the smectic phase, even if there is no chiral group in the molecules. Preliminary experimental data suggest the presence of spontaneous polarization in the nematic phase as well. In order to study the structural properties of the LC phases, X-ray diffraction (XRD) measurements on powder samples have been carried out. Based on the XRD data, a model of the structural arrangement of the bent molecules in the smectic phase is provided, which accounts for the macroscopic spontaneous polarization as well as the ferroelectric switching behavior.     

Properties of BaTiO3/BaZrO3 ferroelectric superlattices with competing instabilities

Properties of (BaTiO₃)₁/(BaZrO₃) _n ferroelectric superlattices (SLs) with n = 1?7 grown in the [001] direction are calculated from first principles within the density functional theory. It is revealed that the quasi-two-dimensional ferroelectricity occurs in these SLs in the barium titanate layers with a thickness of one unit cell; the polarization is oriented in the layer plane and weakly interacts with the polarization in neighboring layers. The ferroelectric ordering energy and the height of the barrier separating different orientational states of polarization in these SLs are sufficiently large to provide the formation of an array of independent polarized planes at 300 K. The effect of the structural instability on the properties of SLs is considered. It is shown that the ground state is a result of simultaneous condensation of the Γ₁₅ polar phonon and phonons at the M point (for SLs with even period) or at the A point (for SLs with odd period); it is a polar structure with out-of-phase rotations of the octahedra in neighboring layers, in which highly polarized layers are spatially separated from the layers with strong rotations. The competition between the ferroelectric and structural instabilities in biaxially compressed SLs manifests itself in that the switching on of the octahedra rotations leads to an abrupt change of the polarization direction and can cause an improper ferroelectric phase transition to occur. It was shown that the experimentally observed z-component of polarization in the SLs can appear only as a result of the mechanical stress relaxation.     

Atomic force microscopic studies of thin oriented films of ferroelectric liquid crystalline elastomers with varying network architecture

Cross-linked ferroelectric liquid crystalline (FLC) polymers were studied by atomic force microscopy (AFM). Polysiloxane copolymers were synthesized with mesogenic and photo-cross-linkable side groups, the latter connected either directly to the backbone via a short spacer or as a terminal group on a part of the mesogens. These elastomers were prepared as thin, freely suspended films in homeotropic orientation. Topographic measurements depict plateaus separated by steps of characteristic height corresponding to the surfaces and edges of smectic layers. From the temperature behavior, as well as from the reaction to mechanical deformation, a model for the network architectures is proposed. In the first case (“intralayer cross-linking”), a predominantly two-dimensional network is formed within the backbone layers separating the smectic layers; in the second case (“interlayer cross-linking”), a three-dimensional network is established that is dependent on the mesophase present during cross-linking.     

‘Guest–host’ effect in liquid crystal mixtures

The most important goal of our research is to show the influence of the ‘guest’ (bent-core mesogen, 1,3-phenyldicarboxylatebis{4-[(4-octylbenzoyl)sulphanyl]phenyl} [IFOS8], banana-shaped liquid crystal [BLC]) on the ‘host’ (calamitic liquid crystal [CLC], (S)-(+)-1-methylheptyloxybiphenyl-(4-n-octylphenyl)thiobenzoate [MHOBS8]), on the stability and the destabilization of the antiferroelectric B2 and the ferroelectric smectic C* (SmC*) phases, and change of the temperature ranges of other phases in the binary liquid crystal mixtures. This work is focused on polymorphism of three new binary liquid crystal mixtures, exhibiting a ‘guest–host’ (guest liquid crystal–host liquid crystal [GH-LC]) effect. MHOBS8 has, among others, a ferroelectric SmC* phase, and IFOS8 assumes the B2 phase with antiferroelectric properties. The observed properties of the mixtures, such as variation of the phase transition temperatures, spontaneous polarization, tilt angle and switching time, are characteristic of a ‘guest–host’ mixture. The influence of BLC on the character of the interactions within the CLC host is discussed, with particular attention paid to electro-optical properties of the GH-LC mixtures.     

A new type of five-ring banana-shaped mesogens with strong dielectric response

Three new homologous bent-shaped mesogens with terminal octyloxy P8, decyloxy P10 and dodecyloxy P12 groups were synthesized. Calorimetric, X-ray and electro-optic investigations prove the existence of two mesophases of the SmCP_A type for compound P10 but only one SmCP_A phase for the homologues P8 and P12. The static dielectric permittivities of compound P12 and that of the low-temperature phase of substance P10 are in the order of 30 and agree with results on bent-core mesogens published before. Surprisingly, the dielectric permittivities of P8 and of the high-temperature phase of P10 are of about 1000. We explain this extremely high dielectric response with the soft reaction of ferroelectric units in the external electrical field.     

Electric-field-induced polar biaxial order in a nontilted smectic phase of an asymmetric bent-core liquid crystal

A polarization reorientation process has been studied by means of optical second-harmonic generation in an optically uniaxial smectic phase of an asymmetric bent-core liquid crystal. A nontilted polar smectic order with a biaxial order is induced by applying an electric field to the uniaxial nonpolar smectic phase. This phenomenon was well simulated by the two-dimensional Langevin process, i.e., electric-field-induced continuous molecular reorientation against thermal agitation. The simulation suggests that about 200s of molecules form a polar domain and cooperatively respond to the applied field. The existence of the polar domains and their reorientation are consistent to the dielectric measurement; a high dielectric constant of about 60 at the kHz range is markedly suppressed by applying a bias field.