Thermotropic Chiral Mesophases

Also classed with cholesteric liquid crystals are the so-called chiral nematics, whose molecules have a composition which is characteristic of nematic liquid crystal molecules but which possess an optical activity, e.g.. 

FIGURE 1.5. (a) The structure of the conventional cholesteric mesophase and (b) a cubic lattice formed by twisted cyUnders which can model one of the blue phases. 

Locally, like nematics, cholesterics are uniaxial. On the macroscopic scale, due to averaging, the helical structure is also uniaxial, the optical axis coinciding with the helical axis which is always perpendicular to the local (nematic) optical axes. Under a microscope, cholesterics can show the focal-conic or finger-print textures. When the helical axis is perpendicular to the limiting glasses, the uniformly colored planar texture is observed. The color depends on the relative value of the pitch Pq with respect to a light wavelength. 

In the vicinity of the transition into the isotropic phase, optically isotropic uniform textures are often observed. These so-called blue phases are cubi-cally symmetric defect structures of cholesteric liquid crystals. With decreasing temperature three blue phases occur [13, 14]. All of them are optically active but not birefringent. The observation of the optical Bragg refiections allowed the determination of the structure of these phases. They are formed by a special packing of pieces of the helix into various cubic lattices. An example is shown in Fig. 1.5(b) [15]. Parameters of the lattices are of the order of the helical pitch. Due to the optical Bragg refiection firom the cubic lattice these phases are blue colored. 

The conventional smectic A phase, formed by chiral molecules and be- 

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To understand how chirality is expressed, it is important to first describe the different thermotropic mesophase assemblies which can be formed by chiral discotics. Even though expression of chirality has been observed in thermotropic mesophases, the chiral expression occurs in a rather uncontrolled manner, and systems which are suitable for applications, for example, easily switchable columns/ferroelectric discotic liquid crystals, consequently have not yet been developed. Hence, the assembly of discotics in solution has received considerable attention. Supramolecular assemblies of discotic molecules in solution are still in their infancy and have not yet found commercial application, but they are of fundamental importance since they allow a detailed and focused investigation of the specific interactions that are required to express chirality at higher levels of organization. As such, the fundamental knowledge acquired from supramolecular assemblies in solution might formulate the design criteria for thermotropic chiral discotic mesophases and provide the necessary tools for the creation of functional systems. 

Figure 6.6 (Left ) Stained section of a crab cuticle Carcinus maenas), showing the single twist of protein fibres (some indicated by red lines), characteristic of the chiral thermotropic cholesteric mesophase. (Right ) Schematic relation between nested arc texture in the micrograph and the cholesteric mesostructure. Micrograph and drawing adapted from (9. ...

Even the first thermotropic liquid crystals (cholesterol benzoate and cholesterol acetate) were chiral molecules, and their chiral mesophases were observed [2]. Here, the chirality is taken from the chiral pool. Because liquid crystals are needed in gram scales for physical research and technical applications, they should be prepared by short synthetic pathways using easily available starting materials. Thus, synthetic strategies based on the chiral pool are more often used than asymmetric synthesis or chiral separation techniques. 

Chiral mesophases can be obtained from sugars by several strategies. Many cellulose derivatives show thermotropic and lyotropic cholesteric phases [16]. Peracylated sugars can be used as chiral dopants for discoid nematic phases [17]. Also classical cholesteric and ferroelectric phases can be obtained from carbohydrate-based compounds [18]. In this case, chiral oxa-heterocycles are prepared from sugars. Figure 4.8 shows a chiral twin compound prepared from mannitol [19]. 

The copper(II) complexes of 1-thio-a- and -i8-D-glucopyranose and 2-amino-2-deoxy-l-thio- -D-glucopyranose and their peracetates have been synthesised by action of copper(II) acetate on the respective sodium thiolates, followed by acid catalysed acetylation, for an investigation of their anti-inflammatory activity The mesogenic properties of the C4 - dialkyl dithioacetals of ten standard pentoses and hexoses have been examined. Most of them form thermotropic liquid crystals with the notable exception of all L-rhamnose derivatives. A model has been proposed to correlate carbohydrate configuration and melting behaviour. Despite the intrinsic chirality of all carbohydrate mesogens no evidence for chiral mesophases was detected. 

It is worth mentioning that the extent of induced circular dichroism on NVC units when inserted in copolymers with intrinsically chiral comonomers is of the same order of magnitude as that extrinsically induced by thermotropic cholesteric mesophases on achiral 9-ethylcarbazole when physically trapped within the mesophase . Higher extrinsic circular dichroism effects are by contrast reported when lyotropic cholesteric mesophases, such as those obtained from polyfy-benzylglutamate) in tetrachloroethane, are used as chiral traps of achiral carbazole derivatives and iso-electronic aromatic compounds ... 

Many cellulose derivatives form Hquid crystalline phases, both in solution (lyotropic mesophases) and in the melt (thermotropic mesophases). The first report (96) showed that aqueous solutions of 30% hydroxypropylceUulose [9004-64-2] (HPC) form lyotropic mesophases that display iridescent colors characteristic of the chiral nematic (cholesteric) state. The field has grown rapidly and has been reviewed from different perspectives (97—101). 

The separation of Hquid crystals as the concentration of ceUulose increases above a critical value (30%) is mosdy because of the higher combinatorial entropy of mixing of the conformationaHy extended ceUulosic chains in the ordered phase. The critical concentration depends on solvent and temperature, and has been estimated from the polymer chain conformation using lattice and virial theories of nematic ordering (102—107). The side-chain substituents govern solubiHty, and if sufficiently bulky and flexible can yield a thermotropic mesophase in an accessible temperature range. AcetoxypropylceUulose [96420-45-8], prepared by acetylating HPC, was the first reported thermotropic ceUulosic (108), and numerous other heavily substituted esters and ethers of hydroxyalkyl ceUuloses also form equUibrium chiral nematic phases, even at ambient temperatures. 

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]. 

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... 

The study of the cholesteric mesophases obtained by doping thermotropic nematics with chiral, nonracemic compounds, has lead to relevant information about the stereochemistry of the dopants. Chiral interactions change the structure of the phase and therefore molecular chirality can be mapped onto an achiral (nematic) phase to yield a superstructural phase chirality. In 1984 Sol-ladie and Zimmermann published the first review summarizing the state of the art at that time.52 Later on, several review articles updated this subject.53-55... 

One of the most classic examples of chiral expression in thermotropic liquid crystals is that of the stereospecific formation of helical fibres by di-astereomers of tartaric acid derivatised either with uracil or 2,6-diacylamino pyridine (Fig. 9) [88]. Upon mixing the complementary components, which are not liquid crystals in their pure state, mesophases form which exist over very broad temperature ranges, whose magnitude depend on whether the tartaric acid core is either d, l or meso [89]. Electron microscopy studies of samples deposited from chloroform solutions showed that aggregates formed by combination of the meso compounds gave no discernable texture, while those formed by combinations of the d or l components produced fibres of a determined handedness [90]. The observation of these fibres and their dimensions makes it possible that the structural hypothesis drawn schematically in Fig. 9 is valid. This example shows elegantly the transfer of chirality from the molecular to the supramolecular level in the nanometer to micrometer regime. 

The arrangement of chiral molecules in thermotropic liquid crystals is more complex, since entire volumes of space - rather than the bounded twisted ribbons discussed above - must be ed subject the constraint of a preferred twist between neighbouring molecules. The simplest examples of such mesophases are the cholesteric liquid crystals, discovered last century, (c/. section 5.1.8). This class of thermotropic liquid crystals derives its generic name from chiral cholesterol derivatives (shown below), which were found a century ago to exhibit peculiar optical changes as they were heated. 

This (local) double twist configuration clearly involves a hyperbolic deformation of the imaginary layers. In contrast to the hyperbolic layers found in bicontinuous bilayer lyotropic mesophases, the molecules within these chiral thermotropic mesophases are oriented parallel to the layers, to achieve nonzero average twist. The magnitude of this twist is deternuned by the direction along which the molecules lie (relative to the principal directions on the surface), and a function of the local curvatures of the layers (K1-K2), cf. eq. 1.4. Just as the molecular shape of (achiral) surfactant molecules determines the membrane curvatures, the chirality of these molecules induces a preferred curvature-orientation relation, via the geodesic torsion of the layer. 

The synthesis and liquid crystalline properties are presented of two classes of chiral (I-n) and prochiral (Il-m) thermotropic poly(ester 0-sulfide)s. The nematic mesophase behavior of the polymers I-n exhibits distinct even-odd alternations with chemical structure and is compared with that of closely related poly(ester 0-sulfide)s Ill-n and IV-m. 

The design and synthesis of new liquid crystalline polymeric materials endowed with intrinsc chirality deserve attention, as chirality can offer probes of the supermolecular structure and a tool for modulating specific responses of the polymers (1). The chemical transformation of preformed thermotropic polymers can add novel opportunities for the realization of various molecular architectures conventionally unfeasible and best suited for mesophase modification. 

Gray, D.G. Harkness, B.R. Chiral nematic mesophase of lyotropic and thermotropic cellulose derivatives. In Liquid Crystalline and... 

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