Thermotropic discotic

Meier et al. have also contributed to the field of cyclic PAV oligomers with the synthesis of cyclic dl -trans (all- ) trimers (e.g. 113) containing alkoxy-substituted 1,7-naphthylene and 1,9-phenanthrylene building blocks, via a Siegrist-type trimerizing olefination [134,135]. Suitable substitution at the periphery of the cyclic trimers allows for the formation of stable, thermotropic discotic mesophases [134]. 

Discotic LC are formed by disk-like molecules with aromatic cores and side chains that are either hydrophobic (i.e., thermotropic) or hydrophilic (i.e., lyotropic). The discotic nematic (No) phase behaves like a normal nematic phase formed by rod-like molecules, and the disk-like molecules are oriented with their short molecular axes parallel to the director but show no positional order. More ordered columnar phases are commonly formed by thermotropic discotics. The two-dimensional structure can pack the columns into a hexagonal or rectangular columnar phase, while within the columns, disks can be... 

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. 14a,b. Columnar arrangement of thermotropic discotics. a) ordered symbol D , b) disordered symbol (Permission for printing)... 

As mentioned above, LLCs, which are columnar stacks of discotic molecules, can be photoaligned, thus forming a thin polarizing layer [61-63], However, the thermotropic discotic LC can also be ordered by a photoalignment method [64-66], A thin film of 25 nm thickness has been prepared on a fused silica surface from a photosensitive polymer with a side-chain p-cyanoazobenzene photosensitive group [64] (Figure 4,22),... 

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. 

Discotic Phases. Molecules which are disk-shaped rather than elongated also form thermotropic Hquid crystal phases. Usually these molecules have aromatic cores and six lateral substituents, although the predominance of six lateral substituents is solely historical molecules with four lateral substituents also can form Hquid crystal phases. Although the flatness of these molecules creates a steric effect promoting alignment of the normal to the disks, the fact that disordered side chains are also necessary for the formation of these phases (as is often the case for Hquid crystallinity in elongated molecules) should not be ignored. 

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]. 

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. 

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. 

Thermotropic liquid crystals, 15 86-98 bent-core, 15 98 discotic phases of, 15 96 frustrated phases of, 15 94-96 metallomesogens, 15 97 nematic liquid crystals, 15 86-92 smectic liquid crystals, 15 92-94 Thermotropic mesophases, 20 79 Thermotropic polycarbonates, 19 804 Thermotropic polyesters, liquid-crystalline, 20 34... 

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). 

It was first reported in the early 1970s that these melt processible polymers could best be described as thermotropic systems which usually display an nematic texture in the melt phase [5]. Subsequently, a number of additional phases have been reported ranging from discotic structures to highly ordered smectic E G systems with three dimensional order. In the last several years an IUPAC sponsored study on nomenclature on thermotropic LPCs has been underway. A more complete set of definitions will be available shortly as a result of Recommendation No. 199 IUPAC [6]. 

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). 

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. 

Isocyanides are excellent ligands for Pd(n) and Pt(ll), to the point that they can be nsed in the synthesis of thermotropic liqnid crystals. Some [MX2(isocyanide)2] complexes are liqnid crystals (discotic) at room temperatnre. The thermal properties depend very mnch on the cis or trans geometry of the complex. For X = I, the trans geometry is favored, whereas for X = Cl, cis complexes are formed. 

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