Discotic mesophases smectic

Fig. 10. Schematic representation of nematic, smectic and discotic mesophases...

Table 2. Examples of Heats and Entropies of Transition of Nematic, Smectic, and Discotic Mesophases...

FIG. 2.16 Schematic representation of the four main types of mesophases. Smectic with ordered (a) and unordered (a ) arrangement of the molecules in layers b) nematic c) cholesteric and d) discotic (from Plate and Shibaev (1987) Courtesy Plenum Press). 

Perhaps one of the most important applications of chiral induction is in the area of liquid crystals. Upon addition of a wide range of appropriate chiral compounds, the achiral nematic, smectic C, and discotic phases are converted into the chiral cholesteric (or twisted nematic), the ferroelectric smectic C and the chiral discotic phases. As a first example, we take the induction of chirality in the columns of aromatic chromophores present in some liquid-crystalline polymers. " The polymers, achiral polyesters incorporating triphenylene moieties, display discotic mesophases, which upon doping with chiral electron acceptors based on tetranitro-9-fluorene, form chiral discotic phases in which the chirality is determined by the dopant. These conclusions were reached on the basis of CD spectra in which strong Cotton effects were observed. Interestingly, the chiral dopants were unable to dramatically influence the chiral winding of triphenylene polymers that already incorporated ste-reogenic centers. 

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. 

The simultaneous occurrence of nematic, cubic, layer and columnar structures in pure mesogens is of great importance to bridging the gap between calamitic and discotic molecules and the corresponding mesophases. Smectic, cubic and columnar phases have also been described in polycatenar compounds, and thus double-swallow-tailed mesogens can also be considered to be a special case of tetracatenar compounds (see Chap. XII of this volume). 

Pecchia, A., Siebbeles, L., Movaghar, B. Chtiige ctirriertrtmsport in higly ordered smectic tmd discotic mesophases. Proc. SPIE 4991, 253—273 (2(X)3)... 

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... 

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). 

Note 5 If the mesogenic side-groups are rod-like (calamitic) in nature, the resulting polymer may, depending upon its detailed structure, exhibit any of the common types of calamitic mesophases nematic, chiral nematic or smectic. Side-on fixed SGPLC, however, are predominantly nematic or chiral nematic in character. Similarly, disc-shaped side-groups tend to promote discotic nematic or columnar mesophases while amphiphilic side-chains tend to promote amphiphilic or lyotropic mesophases. 

Figure 2.19 Orderings in LC mesophases. (a) nematic (b) smectic (c) cholesteric (d) discotic-nematic (e) discotic-columnar.

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... 

Earlier, H-shaped orthometallated palladium(II) complexes were discussed which displayed nematic and smectic phases. However, Praefcke has reported related complexes where the number of chains on the periphery of the molecule is increased leading to columnar mesophases. The complex in Figure 91 displays a monotropic nematic discotic phase (No) and the structure has been confirmed as that in the diagram by single-crystal X-ray crystallography [170]. 

Lyotropic liquid crystals occur abundantly in nature, being ubiquitous in living systems.Their structures are quite complex and are only just beginning to be elucidated. However, in this monograph we shall be confining our attention mainly to the physics of low molecular weight thermotropic liquid crystals and do not propose to discuss polymer and lyotropic systems in any further detail. In chapters 2-5, we deal with the nematic, cholesteric and smectic mesophases of rod-like molecules and in chapter 6 discotic systems. 

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