Thermotropic liquid crystals chiral nematic phase

The prime requirement for the formation of a thermotropic liquid crystal is an anisotropy in the molecular shape. It is to be expected, therefore, that disc-like molecules as well as rod-like molecules should exhibit liquid crystal behaviour. Indeed this possibility was appreciated many years ago by Vorlander [56] although it was not until relatively recently that the first examples of discotic liquid crystals were reported by Chandrasekhar et al. [57]. It is now recognised that discotic molecules can form a variety of columnar mesophases as well as nematic and chiral nematic phases [58]. 

Under just the right conditions, a mixture of a highly polar liquid, a slightly polar liquid, and an amphiphilic molecule form micelles that are not spherical. They can be rodlike, disc-like, or biaxial (all three axes of the micelles are different). These anisotropic micelles sometimes order in the solvent just as liquid crystal molecules order in thermotropic phases. There is a nematic phase of rod-shaped micelles, another nematic phase of disc-shaped micelles, and even a biaxial nematic phase, in which the molecular axes transverse to the long molecular axis partially order. Chiral versions of these phases with the same structure as the chiral nematic phase also form. 

The thermotropic liquid crystal, 4,4 -diheptylazoxybenzene (HAS), exhibiting isotropic, nematic and smectic phases, has been studied through e NMR. The temperature dependence of e chemical shifts and spin-lattice relaxation times of the Xe gas dissolved in HAS showed clear signatures of the phase transitions. Theoretical models have been used to understand the influence of the different phases on the isotropic and anisotropic parts of the chemical shielding. From the studies it is also inferred that in the smectic phase, Xe atoms preferentially occupy interlayer spacings rather than the interiors. Bent-core or banana-shaped molecules display an array of novel chiral liquid crystalline phases. NMR studies on two of the banana core moieties have been analyzed using ab initio structure calculations and the steric inertial frame model. ... 

Cellulose and its derivatives have the ability to behave both as thermotropic and lyotropic liquid crystals. As mentioned above, several specific phases of liquid crystals occurs, depending on the structure or combination of molecules. In the nematic phase, the molecules have only orientational ordering (making the liquid crystal phase less ordered), while in the smectic phase, the molecules have both orientational and positional ordering [75]. In addition, the optically active molecules can form a chiral nematic phase (or cholesteric phase). In this case, the molecules are helix-oriented generating some spectacular optical properties. 

The existence or nonexistence of mirror symmetry plays an important role in nature. The lack of mirror symmetry, called chirality, can be found in systems of all length scales, from elementary particles to macroscopic systems. Due to the collective behavior of the molecules in liquid crystals, molecular chirality has a particularly remarkable influence on the macroscopic physical properties of these systems. Probably, even the flrst observations of thermotropic liquid crystals by Planer (1861) and Reinitzer (1888) were due to the conspicuous selective reflection of the helical structure that occurs in chiral liquid crystals. Many physical properties of liquid crystals depend on chirality, e.g., certain linear and nonlinear optical properties, the occurrence of ferro-, ferri-, antiferro- and piezo-electric behavior, the electroclinic effect, and even the appearance of new phases. In addition, the majority of optical applications of liquid crystals is due to chiral structures, namely the ther-mochromic effect of cholesteric liquid crystals, the rotation of the plane of polarization in twisted nematic liquid crystal displays, and the ferroelectric and antiferroelectric switching of smectic liquid crystals. 

Reinitzer discovered liquid crystallinity in 1888 the so-called fourth state of matter.4 Liquid crystalline molecules combine the properties of mobility of liquids and orientational order of crystals. This phenomenon results from the anisotropy in the molecules from which the liquid crystals are built. Different factors may govern this anisotropy, for example, the presence of polar and apolar parts in the molecule, the fact that it contains flexible and rigid parts, or often a combination of both. Liquid crystals may be thermotropic, being a state of matter in between the solid and the liquid phase, or they may be lyotropic, that is, ordering induced by the solvent. In the latter case the solvent usually solvates a certain part of the molecule while the other part of the molecule helps induce aggregation, leading to mesoscopic assemblies. The first thermotropic mesophase discovered was a chiral nematic or cholesteric phase (N )4 named after the fact that it was observed in a cholesterol derivative. In hindsight, one can conclude that this was not the simplest mesophase possible. In fact, this mesophase is chiral, since the molecules are ordered in... 

Thermotropic cholesterics have several practical applications, some of which are very widespread. Most of the liquid crystal displays produced use either the twisted nematic (see Figure 7.3) or the supertwisted nematic electrooptical effects.6 The liquid crystal materials used in these cells contain a chiral component (effectively a cholesteric phase) which determines the twisting direction. Cholesteric LCs can also be used for storage displays utilizing the dynamic scattering mode.7 Short-pitch cholesterics with temperature-dependent selective reflection in the visible region show different colors at different temperatures and are used for popular digital thermometers.8... 

In addition to thermotropic nematic liquid crystals, others such as chiral, smectic and lyotropic liquid crystals have been investigated and their dynamics and orienting properties studied. The structure of the tilted phase of a chiral liquid crystal has been investigated by means of the line-shape... 

This section pertains to reports on oriented molecules in which phases other than the usual thermotropic nematics have been used. Studies in chiral, smectic, columnar, lyotropic and polymeric liquid crystals as well as other unusual phases have been presented. The use of carbon-proton heteronuclear selective refocusing 2D NMR experiment designed for the spectral analysis of enantiomers dissolved in weakly ordering chiral liquid crystal solvents has been proposed." The method permits the extraction of carbon-proton residual dipolar couplings for each enantiomer from a complex or unresolved proton-coupled... 

Li), the lamellar Ld), and the nematic one (No), which in this case consists of disk-like micelles. One outstanding feature of the system is the extremely wide range of stability of the lamellar as well as of the nematic phase. Moreover, the capability to perform phase transitions lamellar/nematic/ isotropic by temperature variation makes the handling of the samples easy. The short, perfluorinated chains of the surfactant are responsible for the unusual properties of this lyotropic liquid crystal which in some aspects behaves very similar to a thermotropic phase. Both of the briefly introduced achiral lyotropics have been used extensively as host phases for the induction of phase chirality by means of chiral dopants. 

Among the several liquid crystal polymers that have been studied in recent years those containing intrinsically chiral elements with a prevalent chirality hold a particular position. Some of these, in fact, by virtue of their structural characteristics, assume a spatial array with nematic planes stacked in a superhelical structure characterized by a prevalent screw sense and are known as cholesteric phase. This kind of order can be controlled by either concentration in solution (lyotropic systems) or temperature in bulk (thermotropic systems). 

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