Induced smectic phases in phase diagrams of binary nematic liquid crystal mixtures

To elucidate induced smectic A and smectic B phases in binary nematic liquid crystal mixtures, a generalized thermodynamic model has been developed in the framework of a combined Flory-Huggins free energy for isotropic mixing, Maier-Saupe free energy for orientational ordering, McMillan free energy for smectic ordering, Chandrasekhar-Clark free energy for hexagonal ordering, and phase field free energy for crystal solidification. Although nematic constituents have no smectic phase, the complexation between these constituent liquid crystal molecules in their mixture resulted in a more stable ordered phase such as smectic A or B phases. Various phase transitions of crystal-smectic, smectic-nematic, and nematic-isotropic phases have been determined by minimizing the above combined free energies with respect to each order parameter of these mesophases. By changing the strengths of anisotropic interaction and hexagonal interaction parameters, the present model captures the induced smectic A or smectic B phases of the binary nematic mixtures. Of particular importance is the fact that the calculated phase diagrams show remarkable agreement with the experimental phase diagrams of binary nematic liquid crystal mixtures involving induced smectic A or induced smectic B phase.     

Stability of nematic and smectic phases in rod-like mesogens with orientation-dependent attractive interactions

The stability of isotropic (I), nematic (N), smectic A (Sm A), and hexatic (Hex) liquid crystalline phases is studied for a fluid of molecules with a rod-like shape and dispersive interactions dependent on orientation. The fluid is modeled with the spherocylindrical Gay-Berne-Kihara interaction potential proposed in a recent work, with parameters favoring parallel pair orientations. The liquid crystal phase diagram is characterized for different molecular aspect ratios by means of Monte Carlo simulations in the isobaric-isothermal ensemble. Three types of triple points are observed, namely, I-Sm A-Hex, I-N-Sm A, and N-Sm A-Hex, leading to island-shape domains for the smectic A phase. The resulting phase diagrams are compared with those derived previously for prolate fluids of ellipsoidal and spherocylindrical symmetry. It is concluded that the stability of the layered phases with respect to the nematic phase is enhanced in the spherocylindrical fluids due to geometrical constraints. Furthermore, the anisotropy of the dispersive interactions induces a stronger dependence of the overall phase diagram on temperature and aids in the energetic stabilization of the hexatic crystalline phase with respect to the fluid smectic A phase.     

Smectic polymorphism in a series of three-ring enaminoketone compounds

Abstract

Liquid crystalline properties of 1 - (4′ - alkoxyphenylamino) - 3 - (4′ - hexyloxyphenyl)-prop-1-en-3-ones, from methoxy to heptadecyloxy, have been examined by optical, DSC, and X-ray methods. The phase diagram for the series exhibits a rich polymorphism of tilted smectic phases, for example, five mesophases were found for the hexyloxy derivative. A characteristic feature of the phase diagram is a gap in the crystal G phase area. For the heptyloxy homologue, a direct crystal H-smectic F phase transition was found; in the case of shorter as well as longer terminal substituents, the phase sequence crystal H–crystal G–smectic F is observed. Calorimetric and X-ray studies revealed the existence of a tricritical point on the crystal G–smectic F transition line.     

Pretilt angle measurements on smectic A cells with chevron and tilted bookshelf layer structures

We have measured the pretilt angle induced by rubbed polymer films in a smectic A and in a nematic liquid crystalline medium using an optical phase retardation method. The pretilt angle was found to depend on the liquid crystalline phase (smectic A versus nematic) and on the smectic layer structure (chevron versus tilted-bookshelf). The occurrence of the different smectic layer structures was verified by X-ray diffraction measurements. The effect of the applied rubbing energy on the pretilt angle obtained is measured.     

Phase characterization of LC (meth)acrylic monomers based on ω-hexyloxy- and ω-undecyloxy-salicylaldimine groups with different alkoxy tail substitutions

The synthesis and phase characterization of three homologous series of liquid crystalline acrylic and methacrylic monomers, consisting of 21 new compounds are presented. They are based on ω-hexyloxy- and ω-undecyloxysalicylaldimine groups with different alkoxy tail substitutions. The liquid crystalline materials were characterized by polarizing optical microscopy and differential thermal analysis. Smectic A and tilted smectic C phases were observed in the compounds. Near the transition to the isotropic, a narrow nematic phase, coexisting with the smectic A phase, was detected for the pentyloxy and hexyloxy derivatives in the M11 and A11 series. In case of M11R11 and M11R12 only a tilted smectic C phase was detected. The clearing point was comparable for all series, around 100°C.     

New possibility for an organic semiconductor: a smectic liquid crystalline semiconductor having a long conjugated core and two long alkyl chains

We report a new possibility for liquid crystalline organic semiconductors. These materials exhibit smectic liquid crystalline phases, in which the molecules assume a smectic molecular order by self-assembly. Because of the strong dispersion force among long alkyl chains, on cooling, smectic molecular order was retained at room temperature. A charge transport ability was also retained. The conductivity of a device having smectic liquid crystalline order is about 5×10⁷ that of a device with no smectic order. The current - voltage characteristic of the device has a very sharp increase at low threshold voltage (5 V). A high carrier mobility of 1.8×10^-2 was observed in the smectic phase of one of the compounds studied (e).     

New possibility for an organic semiconductor: a smectic liquid crystalline semiconductor having a long conjugated core and two long alkyl chains

We report a new possibility for liquid crystalline organic semiconductors. These materials exhibit smectic liquid crystalline phases, in which the molecules assume a smectic molecular order by self‐assembly. Because of the strong dispersion force among long alkyl chains, on cooling, smectic molecular order was retained at room temperature. A charge transport ability was also retained. The conductivity of a device having smectic liquid crystalline order is about 5×10⁷ that of a device with no smectic order. The current?–?voltage characteristic of the device has a very sharp increase at low threshold voltage (5?V). A high carrier mobility of 1.8×10^‐2 was observed in the smectic phase of one of the compounds studied (e).     

Phase characterization of LC (meth)acrylic monomers based on ω-hexyloxy- and ω-undecyloxy-salicylaldimine groups with different alkoxy tail substitutions

The synthesis and phase characterization of three homologous series of liquid crystalline acrylic and methacrylic monomers, consisting of 21 new compounds are presented. They are based on ω-hexyloxy- and ω-undecyloxysalicylaldimine groups with different alkoxy tail substitutions. The liquid crystalline materials were characterized by polarizing optical microscopy and differential thermal analysis. Smectic A and tilted smectic C phases were observed in the compounds. Near the transition to the isotropic, a narrow nematic phase, coexisting with the smectic A phase, was detected for the pentyloxy and hexyloxy derivatives in the M11 and A11 series. In case of M11R11 and M11R12 only a tilted smectic C phase was detected. The clearing point was comparable for all series, around 100°C.     

De Vries smectic A phase formed by a liquid crystal side chain copolymer? A 13C NMR study

We study the orientation and order parameter of a liquid crystalline random side chain copolymer by ¹³C NMR. Evidence has previously been presented that this material forms a de Vries smectic A phase. The NMR data show that the molecular tilt angle in the smectic A phase is very small or zero and the smectic A–smectic C* transition is attributed predominantly to a change of the molecular tilt rather than azimuthal ordering. We discuss the NMR results in the context of earlier X‐ray and elastic characterizations of structurally similar materials.     

Studies of first- and second-order phase transitions in LC methacrylic monomers based on the ω-hexyloxysalicylaldimine group

The synthesis and phase characterization of two liquid crystalline methacrylic monomers based on the ω-hexyloxysalicylaldimine group with octyl and decyloxy chain substitutions is presented. The liquid crystalline materials were characterized by polarizing optical microscopy, differential thermal analysis and X-ray diffractometry. Nematic and tilted smectic C phases were observed in the compounds. Their liquid crystalline properties where compared with previously studied samples of homologous compounds. In contrast to previous results, this structural modification induces pronounced enantiotropic first-order phase transitions between nematic and smectic C mesophases. A correlation between the phase transition behaviour and structural features of the sample is included.     

New ferroelectric liquid crystalline materials containing one and two lactate groups attached to the molecular core

Several new liquid crystalline materials containing one, two or three chiral centres and having one or two lactate groups in the molecular core have been synthesized. Most of the materials show the blue phase, chiral nematic phase, paraelectric smectic A phase and orthogonal hexatic smectic B phase; some possess the ferroelectric SmC* phase. A study of the mesomorphic properties has been performed using differential scanning calorimetry, optical microscopy and X-ray diffraction. The thickness of the smectic layers and the value of the average distance between the long axes of neighbouring molecules were determined. In the SmC* phase, the temperature dependence of spontaneous polarization, spontaneous tilt angle and helical pitch was measured. The influence of the number of lactate groups on mesogenic behaviour has been established.     

De Vries smectic A phase formed by a liquid crystal side chain copolymer? A 13C NMR study

We study the orientation and order parameter of a liquid crystalline random side chain copolymer by ¹³C NMR. Evidence has previously been presented that this material forms a de Vries smectic A phase. The NMR data show that the molecular tilt angle in the smectic A phase is very small or zero and the smectic A-smectic C* transition is attributed predominantly to a change of the molecular tilt rather than azimuthal ordering. We discuss the NMR results in the context of earlier X-ray and elastic characterizations of structurally similar materials.     

Broad band dielectric relaxation spectroscopy of molecular reorientation in smectic liquid crystalline phases (SmA, SmB, and CrE)

Broad band dielectric measurements reveal that the reorientation of non-chiral rod-shaped low molecular mass liquid crystals is active around their molecular long axis and a short axis, in the smectic A and hexatic smectic B phase, respectively, as well as in the soft crystalline E phase of two isomeric stilbene compounds possessing an equal molecular length of their all-trans -conformations. One ('generalized') Arrhenius equation describes the temperature dependence of the reorientation around a molecular short axis for each of these phases of both compounds. A change of the activation energy related to the reorientation around a molecular short axis is accompanied by a slowing down of the reorientation around the molecular long axis in the soft crystalline E phase in one of these compounds, compelling evidence for a coupling of both reorientations. This result is discussed with respect to the biaxiality of the soft crystalline E phase.     

Ionic liquid crystals derived from the protonation of poly(propylene imine) dendrimers with a cholesterol-based carboxylic acid

The liquid crystalline character of salts resulting from the interaction of poly(propylene imine) dendrimers with 3-cholesteryloxycarbonylpropanoic acid has been studied. The supramolecular structure and consequently the observed liquid crystalline phases are dictated by the degree of protonation of primary amino groups as compared with that of tertiary ones, determined by FTIR spectroscopy in the bulk and by NMR spectroscopy in solution. Glass transition temperatures of the materials are about 38°C. At higher temperatures they are transformed to smectic C* phases while a second-order smectic C phase to smectic A phase transition is observed between 90 and 110°C depending on dendrimer generation. At about 150°C the onset of degradation is observed. The influence of the ionic dendrimeric scaffold on the thermotropic properties is discussed.     

Chemical reactivity within a smectic B liquid crystalline phase: A model of enzyme catalysis?

The rearrangement of allyl p-dimethylaminobenzenesulphonate (ASE) to form a zwitterionic product has already been recognized as an effective probe for the study of reactivity within the smectic B phase [4, 5, 19]. We have used deuterium NMR, linear dichroism and X-ray diffraction techniques to investigate the phase diagram of the ASE-OS35 reaction system. The partitioning of the reactant molecules between coexisting smectic, nematic and/or isotropic phases and the structural organization of the smectic catalytic host at different temperatures and reactant guest concentrations have been characterized. On the basis of these measurements, a model of ASE reactivity in smectic solvents has been developed. The reaction takes place provided that coexisting isotropic or nematic phases are present to act as a reservoir for the ASE reactant molecules prior to their entering the smectic phase; they then react and leave the smectic phase as a zwitterionic product. The analogy between this model of reactivity within smectic phases and the Michaelis-Menten enzyme processes is discussed. This relationship opens up the intriguing possibility of designing new experiments with which to investigate further liquid crystalline models of enzyme catalysis.     

Ionic liquid crystals derived from the protonation of poly(propylene imine) dendrimers with a cholesterol-based carboxylic acid

The liquid crystalline character of salts resulting from the interaction of poly(propylene imine) dendrimers with 3-cholesteryloxycarbonylpropanoic acid has been studied. The supramolecular structure and consequently the observed liquid crystalline phases are dictated by the degree of protonation of primary amino groups as compared with that of tertiary ones, determined by FTIR spectroscopy in the bulk and by NMR spectroscopy in solution. Glass transition temperatures of the materials are about 38°C. At higher temperatures they are transformed to smectic C* phases while a second-order smectic C phase to smectic A phase transition is observed between 90 and 110°C depending on dendrimer generation. At about 150°C the onset of degradation is observed. The influence of the ionic dendrimeric scaffold on the thermotropic properties is discussed.     

Theoretical simulation of thermally induced phase separation in a main‐chain liquid‐crystalline polymer solution

Phase diagrams of main‐chain liquid‐crystalline polymer (MCLCP) solutions have been calculated self‐consistently on the basis of a simple addition of the Flory–Huggins free energy for isotropic mixing, the Maier–Saupe free energy for nematic ordering, and the Flory free energy for chain rigidity of the MCLCP backbone. The calculated phase diagram is an upper critical solution type overlapping with the nematic–isotropic transition. The phase diagram consists of liquid–liquid, liquid–nematic, and pure nematic regions. Subsequently, the dynamics of thermally induced phase separation and morphology development have been investigated by the incorporation of the combined free energy density into the coupled time‐dependent Ginzburg–Landau (model C) equations, which involve conserved compositional and nonconserved orientational order parameters. The numerical calculations reveal a variety of the morphological patterns arising from the competition between liquid–liquid phase separation and nematic ordering of the liquid‐crystalline polymer. Of particular interest is the observation of an inflection in the growth dynamic curve, which may be attributed to the nematic ordering of the MCLCP component, which leads to the breakdown of the interconnected domains. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 913–926, 2003     

液晶金属配位聚合物的合成及性能

基于国内外最新研究文献 ,系统论述了近年来液晶金属配位聚合物的合成方法、液晶行为及应用前景。指出液晶金属配位聚合物的合成方法可归纳为直接配位法、单体配位法、交联配位法和聚合物反应法四种。液晶金属配位聚合物一般呈现热致液晶行为 ,显示稳定的向列液晶相或近晶液晶相。有些金属配位聚合物还呈现互变性近晶态或单变液晶性。液晶金属配位聚合物具有金属的特殊性质 ,是一种新型高性能磁导、电导和光导材料 ,可望应用于液晶显示材料、磁性信息储存薄膜材料、润滑剂和各向异性催化剂等。     

Stripe instabilities in the menisci of free-standing smectic films: influence of the phase sequence of the mesogenic material

We briefly report experimental observations of striped patterns in the menisci of free-standing smectic C films. The results were obtained with a mesogenic compound that transits directly from the nematic phase to the smectic C phase, without an intermediate smectic A phase. In this case, it is shown that stripes do not correspond to undulations of the smectic free surface and smectic layers, as was indeed evidenced in previous studies with other compounds and different phase sequences. Hence, our results show that the nature of striped patterns in free-standing films depends on the phase sequence of the considered materials. Further experimental and theoretical works are still required to fully elucidate the physical mechanisms that drive the onset of patterns in such systems.