Main Calamitic Phases

FriedeP was the first who distinguished three main classes of liquid crystals, according to the different kind of orders in the mesophases nematic, smectic, and cholesteric. From the point of view of the geometrical shape of molecules, we divide the thermotropic LCs into calamitic phases (when the molecules are rodlike), sanidic phases (when the molecules are bricklike), and the discotic phases (when the molecules are disklike)... 

Referring to the nomenclature defined in Table 1.1, we shall encounter mainly one-comb, double-comb, parallel (and biparallel) and network LCPs that exhibit calamitic phases (such as smectic and nematic). Calamitic phases result from mesogens that are lath-shaped. We shall... 

Thennotropic liquid crystal phases are fonned by anisotropic molecules witli long-range orientational order and in many types of stmcture witli some degree of translational order. The main types of mesogen are Arose tlrat are rodlike or calamitic and Arose Arat are disclike or discotic. 

Calamitic mesogens in general form two main types of mesophase the nematic phase (N) and the smectic (S) phases. The nematic phase is the most disordered of the mesophase tjpes in it, the molecules possess one-dimensional orientational order and no positional order (Fig. 22). 

Liquid crystallinity can be attained in polymers of various polymer architectures, allowing the chemist to combine properties of macromolecules with the anisotropic properties of LC-phases. Mesogenic imits can be introduced into a polymer chain in different ways, as outhned in Fig. 1. For thermotropic LC systems, the LC-active units can be connected directly to each other in a condensation-type polymer to form the main chain ( main chain liquid crystalline polymers , MCLCPs) or they can be attached to the main chain as side chains ( side chain liquid crystalline polymers , SCLCPs). Calamitic (rod-Uke) as well as discotic mesogens have successfully been incorporated into polymers. Lyotropic LC-systems can also be formed by macromolecides. Amphiphihc block copolymers show this behavior when they have well-defined block structures with narrow molecular weight distributions. 

Thermotropic liquid crystals can then be furflier subdivided into high molecular mass, main and side-chain polymers [10] and low molecular mass, the latter class of compounds being one of the areas of this review. The phases exhibited by the low molecular mass molecules are then properly described with reference to the symmetry and/or supramolecular geometry of the phases, which are briefly introduced here and are discussed in more detail further below. Thus, the most disordered mesophase is the nematic (N), which is found for calamitic molecules (N), discoidal molecules (Nq) and columnar aggregates (Nc), among others. The more ordered lamellar or smectic phases (S) [11, 12] are commonly shown by calamitic molecules, and there exists a variety of such phases distinguished by a subscripted letter (e. g. Sa, Sb)- Columnar phases (often, if incorrectly, referred to as discotic phases) may be formed from stacks of disc-like molecules, or from... 

Figure 20. (a) Orientational correlation time t in the logarithmic scale as function of the inverse of the scaled temperature, with the scaling being done by the isotropic to nematic transition temperature with Ti-N. For the insets, the horizontal and the vertical axis labels read the same as that of the main frame and are thus omitted for clarity. Along each isochor, the solid line is the Arrhenius fit to the subset of the high-temperature data and the dotted line corresponds to the fit to the data near the isotropic-nematic phase boundary with the VFT form, (b) Fragility index m as a function of density for different aspect ratios of model calamitic systems. The systems considered are GB(3, 5, 2, 1), GB(3.4, 5, 2, 1), and GB(3.8, 5, 2, 1). In each case, N = 500. (Reproduced from Ref. 136.)... 

Similarly to the molecular engineering of calamitic molecules to produce ferroelectric smectic C phases [129], disk-like molecules with chiral peripheral chains tilted with respect to the columnar axis were predicted to lead to ferroelectric columnar mesophases [130]. Indeed, as it is the case with all flat disk-shaped mesogenic molecules, the tilt is mainly associated with the flat rigid aromatic cores of the molecules, the side-chains being in a disordered state around the columnar core. Thus, the nearest part of the chains from the cores makes an angle with the plane of the tilted aromatic part of the molecules. If the chiral centre and the dipole moment are located close to the core, then each column possesses a non-zero time averaged dipole moment, and therefore a spontaneous polarization. For reasons of symmetry, this polarization must be, on average, perpendicular to both the columnar axis and to the tilt direction in other words, the polarization is parallel to the axis about which the disk-shaped molecules rotate when they tilt as shown in Fig. 29. 

Many bent-core molecules do not have nematic phases, but may be added to calamitic nematics to tune the flexoelectric behaviour. Several groups have reported measurement results in such guest-host systems ° using either HAN cells or the flexoelectro-optic effect mentioned above. It was found that some BC compounds used as dopants in small (< 10%) concentration may effectively increase ei —es of the host. ° Other, mainly asymmetric, BC compounds had hardly any influence on ei - - es of the host nematic. ... 

This chapter presents a review of different liquid crystal phases. The main attention is paid to the thermotropic liquid crystals, which manifest rich polymorphism upon variation of temperature. Moreover, the thermotropic phases are subdivided into rod-like or calamitic and discotic ones the latter are discussed only briefly. At first, we discuss achiral media with lyotropic phases included and then consider the role of chirality. 

The most important multicolour display technology in current use involves liquid crystal displays (LCDs), which overtook CRTs in popularity around the mid-2000s. Liquid crystals (LCs), commonly referred to as the fourth state of matter, are materials that are intermediate in character between the crystalline solid and liquid states.Unlike normal isotropic liquids in which the molecules essentially adopt a randomised orientation, liquid crystals show some time-averaged positional orientation of the molecules. In this sense, they resemble solid crystalline materials, although they retain most of the properties of liquids, notably the ability to flow. They are formed most commonly from molecules with rod-like geometry, which are referred to as calamitic. These molecules may orientate in various ways to form different types of LC phases [mesophases). There are three main mesophase types smectic, nematic and chiral nematic. In the smectic mesophase, as illustrated in Figure 11.1(a), the molecules are arranged in raft-like layers with their molecular axes parallel. These layers can pass over each other as the material flows. In the... 

Fig. 3.1 Building blocks of thermotropic and lyotropic liquid crystalline phases. The upper part of the figure shows two examples of typical thermotropic mesogens. Calamitic mesogens, such as terephthal-bis-(p-butylaniline) (TBBA) [2], can be represented by prolate ellipsoids or rigid rods, while discotic mesogens, such as benzene-hexa-n-octanoate (BH8) [4], are usually described by oblate ellipsoids or discs. The lower part of the figure shows the typical surfactant molecule sodium dodecyl sulfate (SDS), which forms lyotropic phases with water [5], Such a surfactant molecule is basically composed of a polar head group and a flexible hydrophobic tail. These amphiphilic molecules aggregate into different types of micelles, which are the actual mesogens of lyotropic liquid crystals. The shape of the micelles depends mainly on the solvent concentration...

Main ehain liquid crystalline polymers can be constructed from rod-like (calamitic) and disc-like (discotic) units by a condensation process (see Chapter 8). Seen here in racemic form, polymer 11 is a poly ether with repeating mesogenic-like core units separated by flexible alternating hydrocarbon spacers. This typical architecture ensmes a sufficiently low melting point for liquid crystalline phases to be exhibited. Polymer 11 has a molecular weight of 17,000 and a polydispersity of 1.7. 

Substances that show a liquid crystalline phase, or mesophase, are called mesogens. Several thousands of compounds, both with low molecular mass and polymeric, are now known to form mesophases. They are mainly highly geometrically anisotropic in shape, rodlike or disclike (hence the terms calamitic and discotic liquid crystals), or they are anisotropic in solubility properties, like amphiphilic molecules and, depending on their detailed molecular structure, they can exhibit one or more mesophases between the crystalline solid and the isotropic liquid. Transitions to these intermediate states may be induced by purely thermal processes (thermotropic liquid crystals) or by the action of solvents (lyotropic liquid crystals). Each of these two categories can be further divided according to the structure of the mesophases and/or molecules Scheme 1 shows the classification of thermotropic mesophases. 

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