Thermotropic calamitic liquid crystals

Figure 2.6 The molecular structure of a typical calamitic, thermotropic nematic liquid crystal. The diameter of the molecule measured in the x-y plane is symmetrical about the z-axis due to very rapid rotation about the molecular long axis.

Another example where the amphipathic feature of the molecules plays an important role is the case of some thermotropic ionic calamitic liquid crystals such as ditholium salts [64]. In spite of their rod-like shape, these compounds exhibit columnar mesophases with supramolecular organization similar to that of amphiphilic molecules. In this case, it is clear that the driving force for the supramolecular organization is the amphipathic character of the molecules... 

A thermotropic liquid crystal is capable of polymorphism, the situation in which a material exhibits more than one liquid-crystalline modification between the solid and liquid phases. For instance, when a calamitic liquid crystal melts it can do so via transitions between a number of smectic phases and the nematic phase. For the purposes of phase... 

Figure 1.10. Typical phase sequence in thermotropic liquid crystals. Top Calamitic liquid crystals (consisting of rod-like molecules) Bottom Discotic liquid crystals (consisting of disk-shaped molecules).

Thermotropic liquid crystals are composed of moderate-size ( 2-5nm) organic molecules, which are strongly anisometric elongated and shaped like a cigar (so-called calamitic liquid crystals), disc-shape (discotic LCs), or bent-shape (pyramidal or banana-shape). 

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. 

Many technological applications of liquid crystals, as in electro-optic display devices, are based on multicomponent mixtures. Such systems offer a route to the desired material properties which cannot be achieved simultaneously for single component systems. Mixtures also tend to exhibit a richer phase behaviour than pure systems with features such as re-entrant nematic phases [3] and nematic-nematic transitions possible. In this section, we describe simulations which have been used to study mixtures of thermotropic calamitic mesogens. 

The mesophases of thermotropic liquid crystals are described as calamitic if the constituent molecules are rod-like and columnar, if the constituent molecules, which often have a disc like shape(discotic), stack into columns. 

FIG. 2. Schematic representation of different calamitic and discotic thermotropic liquid crystals (a) nematic, (b) cholesteric, (c-e) smectic, (f) columnar hexagonal, (g) columnar hexagonal tilted a-e adapted from Demus, D., and Richter, L., Textures of Liquid Crystals, Verlag Chemie, Weinheim, Germany, 1978 f,g adapted from Eidenschenk, R., Flussige Kristalle, Chem. Unserer Zeit, 18, 168-176 (1978). 

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). 

Fig. 2 Schematic representation of different calamitic and discotic thermotropic liquid crystals. (A) nematic (B) cholesteric (C-E) smectic (F) columnar hexagonal (G) columnar hexagonal tilted. (A-E Adapted from Ref F and G Adapted from Ref. l)...

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... 

The cubic phase is still a rather rare observation in thermotropic liquid crystal systems, and is foimd in conventional calamitic materials, as well as in polycatenar materials vide infra). It is a viscous, optically isotropic phase whose kinetics of... 

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