Discotic liquid crystals columnar structures

Discotic liquid crystals arise from disk-shaped molecules as nematic or cholesteric mesophases. Their structural characteristics are similar to the respective ealamitie mesophases, that is, the normals of the disks are oriented parallel. Instead of the smectic mesophases, diseotie columnar liquid crystals arise from eonnecting the disks to each other. The columns of the discotic columnar mesophase form a two-dimensional lattice whieh is in a hexagonal or rectangular modification. In addition, the columns may be tilted (Fig. 2f,g). 

In contrast to calamitic mesogens, discotic liquid crystals are built from disk-like molecules that can arrange into different structures, such as the discotic nematic mesophase, the discotic columnar mesophase, or the discotic hexagonal meso-phase. 

Chandrasekhar S 1998 Columnar, discotic, nematic and lamellar liquid crystals Their structures and physical properties Handbook of Liquid Crystals Vol 2B. Low Molecular Weight Liquid Crystals I ed D Demus, J Goodby, G W Gray, H-W Spiess and V Vill (New York Wiley-VCH)... 

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... 

Fig. 6.4.2. The discotic liquid crystal appearing in the isotropic phase when a sample is cooled very slowly. The growth pattern is diagnostic of the hexagonal symmetry of the columnar structure (a) Queguiner, Zann and Dubois , (b)...

Fig. 7.8 Magnetic alignment of discotic liquid crystals, a Molecular structure of a discotic compound and b an arrangement of columnar stacks perpendicular to the magnetic field on a substrate. Reproduced with permission from [142]. Copyright 2006 Elsevier...

Figure 1 General structures of calamitic and discotic thermotropic liquid crystals. (A) Layered calamitic smectic liquid crystal. The structures of the various types depend on the local packing of the molecules, the extent of the packing, and the orientation of the long axes with respect to the layers. (B) Calamitic nematic liquid crystal. The molecules have no long-range order, and are only orientationally ordered. (C) Ordered columnar discotic liquid crystal. Disk-like molecules form ordered or disordered columns different column packings give rise to various mesophase structures. (D) Nematic-discotic liquid crystal phase. The disk-like molecules are only orientationally ordered.

The nomenclature of discotic liquid crystals depends on the arrangement of the compounds (molecules) in columnar or nematic structures. Within a short spatial range and in the temporal and spatial average the longitudinal axes of nematic molecules are oriented parallel to each other. 

Columnar Structures from Discotic Liquid Crystals. 174... 

Solid state NMR, however, is probably even more powerful for probing the time scale and geometry of rotational motions [14]. For instance, disk-shaped aromatics often stack into columnar structures as part of discotic liquid crystals (DEC)... 

The orthogonal arrangement of the disc-like molecules in the columns of and D id phases makes these phases uniaxial, while the tilted phases (Drd and Doh.d and Dt) are optically biaxial. There are two additional columnar phases labeled as and that have not yet been classified. The columnar phases were discovered before the observation of a nematic phase for disc-like molecules. Both chiral nematic phases and the re-entrant behavior have now been observed in discotics. The phase diagram and molecular structure of a typical discotic liquid crystal are shown in Fig. 1.11. Finally, it is noted that another classification scheme for the discotic mesophases has been used [1.26], which is based on the notation used for the conventional smectics. 

To some degree problems of notation did arise with the naming of columnar meso-phases. Originally they were called discotic liquid crystals, and indeed they also acquired a crystallographic notation. Both of these notations have, however, fallen out of favor and the naming of the state has been redefined. As research in disc-like systems remains relatively active, it is to be expected that further phases will be discovered, and as our understanding of the structures of these phases increases changes may be made to our current notation. 

Columnar, Discotic Nematic and Lamellar Liquid Crystals Their Structures and Physical Properties... 

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... 

Another class of liquid crystal materials that has been studied extensively is the discotic liquid crystal. As the name implies, these phases form from disk-shaped molecules. A material showing this behavior was first identified and studied in 1977 by Chandasekar. Examples of some typical discotic molecular structures are shown in Figure 2.19. There are two main classes of discotic phase, the nematic and columnar discotic phases schematics of these phases can be seen in Figure 2.20. The nematic discotic... 

As discussed in Chaps. 3 and 4, (columnar) discotic liquid crystals are oriented in columns separated by molten aliphatic chains and, consequently, they can conduct charge efficiently along the channels in one dimension. The organization of the different phases is described elsewhere [19, 20] and the efficiency of charge transport can be directly related to the short intermolecular spacing and order of different types of mesophase, with few exceptions [21]. For example, hole mobility is higher in ordered, rather than disordered, columnar phases and even higher in helically-ordered phases where molecular rotation is suppressed about the columnar axis [22], Some mesomorphic derivatives of hexabenzocoronene, for example hexaphenyl-substituted hexabenzocoronene (HBCn, see Table 8.2 for chemical structures of all discotic materials discussed here) have hole mobilities... 

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