Thermotropic liquid crystals discotic mesogens

Of all liquid crystalline phases, the nematic phase is the phase with the highest symmetry, i.e. Dooh, and the least order. As shown in Fig. 3.3a, b, the mesogens solely possess orientational order. Positional order of the mass centers does not occur in this phase. Nematic phases are usually built up by either rod-like or disc-like mesogens. For thermotropic liquid crystals these mesogens are therefore calamitic or discotic molecules, respectively. In both cases the phase is simply denoted with the abbreviation N. For lyotropics, the notation typically distinguishes between nematic phases Nc, which are formed by rod-like micelles, and nematic phases Np, which are composed of disc-like micelles. 

Thermotropic liquid crystals come in two types calamitic and discotic. Calamitic phases (from the Greek for tube ) are all those that are caused by rod-like mesogens. The more recently characterised discotic phases are caused by disc-like species. Calamitic phases may be either nematic (from the Greek for thread ), smectic (from the Greek for soap ) or cholesteric (named after the cholesterol derivatives such as 13.4, which exhibit this behaviour). 

Thermotropic Liquid Crystals. - Organic molecules, having aromatic rings or unsaturations thus producing elongated shapes, and also polymeric molecules often show thermotropic phase behavior. Mesomorphism comprises typically nematic, smectic A and B, and cholesteric thermotropic phases, but in several cases columnar, discotic and rod-disk self-assembly shapes of thermosensitive mesogens have been observed. 

Columnar phases are typically formed by either thermotropic liquid crystals made up of discotic mesogens stacking upon each other to form columns or by lyotropic liquid crystals composed of rod-like micelles. These columns or rods arrange into two-dimensionaUy correlated structures. Alongside the long axis of the columns... 

Thermotropic liquid crystal phases are formed by anisotropic molecules with long-range orientational order, and in many types of structure some degree of translational order. The main types of mesogens are those that are rod-like or calamitic and those that are disc-like or discotic. 

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. 

Liquid crystals may be divided into two broad categories, thermotropic and lyotropic, according to the principal means of breaking down the complete order of the soHd state. Thermotropic Hquid crystals result from the melting of mesogenic soHds due to an increase in temperature. Both pure substances and mixtures form thermotropic Hquid crystals. In order for a mixture to be a thermotropic Hquid crystal, the different components must be completely miscible. Table 1 contains a few examples of the many Hquid crystal forming compounds (2). Much more is known about calamitic (rod-Hke) Hquid crystals then discotic (disk-like) Hquid crystals, since the latter were discovered only recendy. Therefore, most of this section deals exclusively with calamities, with brief coverage of discotics at the end. 

Understanding the organization of disc-shaped mesogens in columnar phases is of practical interest because of their useful optoelectronic applications [168-170]. It will be instructive to explore the role of fluctuations in influencing transport properties of thermotropic discotic liquid crystals—in particular, in the columnar phase. 

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...

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