Discotic liquid crystals disc-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). 

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]. 

Discotic liquid crystals The molecules possess a disc shape in many cases they are polysubstituted benzene or triphenyl derivatives with lateral extended aliphatic chains. These molecules arrange, e.g., in large columns a discotic nematic phase is known too. 

Discotic liquid crystals arise from disc-shaped molecules as nematic or cholesteric mesophases. Their structural characteristics are similar to that of their respective calamitic mesophases, that is, the normals... 

The first liquid crystals of disc-shaped molecules, now generally referred to as discotic liquid crystals, were prepared and identified in 1977. Since then a large number of discotic compounds have been synthesized and a variety of mesophases discovered. Structurally, most of them fall into two distinct categories, the columnar and the nematic. The columnar phase in its simplest form consists of discs stacked one on top of the other aperiodically to form liquid-like columns, the different columns constituting a two-dimensional lattice (fig. 1.1.8 (a)). The structure is somewhat similar to that of the hexagonal phase of soap-water and other lyotropic... 

The subject of liquid crystals has now grown to become an exciting interdisciplinary field of research with important practical applications. This book presents a systematic and self-contained treatment of the physics of the different types of thermotropic liquid crystals - the three classical types, nematic, cholesteric and smectic, composed of rod-shaped molecules, and the newly discovered discotic type composed of disc-shaped molecules. The coverage includes a description of the structures of these four main types and their polymorphic modifications, their thermodynamical, optical and mechanical properties and their behaviour under external fields. The basic principles underlying the major applications of liquid crystals in display technology (for example, the twisted and supertwisted nematic devices, the surface stabilized ferroelectric device, etc.) and in thermography are also discussed. 

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...

States exist in which the molecules have long range translational order in some respects but disorder in others. These are called liquid crystals. Liquid crystals exhibit fluid flow but are anisotropic. Transitions in which at least one phase is a liquid crystal are mesomorphic transitions. Compotmds of relatively long rod-shaped molecules with polar groups form tluee main types of liquid ciystals. They are nematic, cholesteric, and smectic. Disc-shaped molecules may also form several types of liquid crystals having the general designation of discotic. 

In contrast it was shown in the past years that discotic liquid crystals like hexapenty-loxytriphenylene (HPT) 23 have carrier mobilities up to 10 cm A s in the liquid crystalline I o phase [10]. Here, the disc-shaped molecules are ideally stacked above each other and therewith allow a fast carrier transport. The discotic hexathioether 24 with a highly ordered helical columnar (H) phase exhibits mobilities up to 10 cm A s, which are almost as high as in organic single crystals [11]. 

The knowledge base in fundamental science was also extended greatly by the discovery in Chandrasekhar s group [60] of liquid crystals formed by disc-shaped molecules. Capable of forming discotic nematic phases and a range of columnar phases, these materials currently attract much interest and technological applications for them are possible. 

We start by reminding ourselves that columnar discotic liquid crystals are comprised of disordered stacks (1-dimensional fluids) of disc-shaped molecules arranged on a two-dimensional lattice (Fig. 1) [1]. This structure imparts novel properties to these materials from which applications are likely to stem. One such property is the transport of charge along the individual molecular stacks [2-7]. The separation between the aromatic cores in, for example, the hexa-alkoxytriphenylenes (HATn), the archetypal columnar discotic mesogen, is of the order of 0.35 nm, so that considerable overlap of n orbitals of adjacent aromatic rings is... 

Until 1977, it was believed that only rod-like molecules, having a considerably higher length than width, could show liquid crystalline properties (calamitic mesogens). However, in 1977, Chandrasekhar realized that not only rod-like molecules, but also compounds with a disc-like molecular shape are capable of forming mesophases (Chandrasekhar et al. 1977 Sabine et al. 2007) and these are referred to as discotic liquid crystals (DLCs). The first examples of this kind of mesomorphism were observed in hexa-alkanoyloxybenzenes, hexaalkoxy- and -aUcanoyloxy-triphenylenes (Fig. 16.2), and were established by X-ray studies (Kumar 2010). Generally, the disc shaped molecules have central core as benzene or polyaromatic, such as triphenylene or phthalocyanine. 

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. 

Liquid-crystalline phases are characterized to some degree by the shape of the molecules and by their packing arrangements and ordering in the mesomorphic state. Typically, molecules can have cither disc- or rod-like shapes and can form discotic or calamitic mesophases, respectively. Ferrocene liquid crystal systems that have so far been synthesized tend to have molecular structures that are lath- or rod-like in shape, and consequently the phases observed are calamitic. However, this does not preclude the possibility that a polysubstituted ferrocene could be prepared where the molecular shape is disc-like, thereby holding out the prospect of possibly producing discotic/columnar phases. 

There are several different phases in thermotropic liquid crystals. The structural nature of mesophases is influenced by the molecular shape and therefore depends on whether the liquid crystal is formed by rod-like or disc-like molecules. Thermotropics of rod-like molecules may be divided into two main categories nematic and smectic phases. There exist many types of smectic phases, labeled as 5, 5b, S /. When an ordered solid of a liquid crystal melts (see Fig. 1.1), it may melt into a nematic phase or a smectic A phase. Upon further heating, it eventually turns into an isotropic liquid. First, classical thermotropic liquid crystals are described, and then a group of more exotic liquid crystals like discotic thermotropics, lyotropics, and liquid crystalline polymers. 

The second group comprises thermotropic polymers. The phase transitions of thermotropic liquid crystals are achieved when a determined temperature range is reached. The fundamental unit that induces structural order in this kind of polymer presents with high rigidity and anisotropic shape [26,27]. Two major subclasses can be distinguished according to this shape discotic (disc-Uke molecules) and... 

Comparable to the nematic (N) phase of rod-like compounds the least orda ed (usually highest temperature) mesophase exhibited by disc-like molecules is also the nematic (discotic. No) phase the index D simply refers to their molecular shape. Both nematic phases are of the same symmetry and identical types of defects are seen in both cases [5] they exhibit similar fluid Schlieren textures [3,6]. However, the nematic phases of these two low-molar-mass liquid crystals are not miscible [3,6] and phase separation occurs due to fundamental differences in their molecular structures. 

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