Thermotropic calamitic

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. 

Note 4 The situation for thermotropic calamitic systems is less clear and for some compounds claimed to form a Nb, detailed investigations have found the mesophase to be of type Nu. 

Copolymeric systems with amylose are therefore systems in which at least one component is based on a conformationally rigid segment, which are generally referred to as rod-coil systems." By combining rod-like and coillike polymers a novel class of self-assembling materials can be produced since the molecules share certain general characteristics typical of diblock molecules and thermotropic calamitic molecules. The difference in chain rigidity of rod-... 

In the following sections some of the more common liquid crystal textures utilized in the classification of thermotropic calamitic mesophases are described. It should be noted that similar examinations of defects are used to classify discotic, polymeric, and lyotropic phases. 

There are some specific amphiphile systems which form exceptionally stable pancake-like micelles which, as one might expect, give anisotropic solutions analogous to discotic nematic phases. Conversely, there are other lyotropic systems containing elongated stacks of aromatic molecules, i.e., chromonic systems, which are analogous to thermotropic calamitic nematic phases. 

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. 

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. 

Thermotropic liquid crystalline (LC) phases or mesophases are usually formed by rod-like (calamitic) or disk-like (discotic) molecules. Spheroidal dendrimers are therefore incapable of forming mesophases unless they are flexible, because this would allow them to deform and subsequently line up in a common orientation. However, poly(ethyleneimine) dendrimers were reported to exhibit lyotropic liquid crystalline properties as early as 1988 [123],... 

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). 

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.

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. 

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... 

It is well known that the connection of oligo(alkylene ether) chains into a calamitic rigid rod at the terminals destabilizes the thermotropic meso-phases [8]. However, mesomorphic properties can be obtained by molecules with extended rigid rod segments as a result of the microphase segregation between the polar flexible oligo(alkylene oxide) ethers and rigid rod seg-... 

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