Hexagonal columnar phases, discotics

McMillan s model [71] for transitions to and from tlie SmA phase (section C2.2.3.2) has been extended to columnar liquid crystal phases fonned by discotic molecules [36, 103]. An order parameter tliat couples translational order to orientational order is again added into a modified Maier-Saupe tlieory, tliat provides tlie orientational order parameter. The coupling order parameter allows for tlie two-dimensional symmetry of tlie columnar phase. This tlieory is able to account for stable isotropic, discotic nematic and hexagonal columnar phases. 

Pyridone forms a hydrogen-bonded dimer with a closed structure [136]. This dimerization has been used for the design of crystalline assemblies such as three-dimensional networks [136b]. This hydrogen bonding has been used for the formation of discotic liquid-crystalline assemblies [137]. Disk-like complex 58 with dodecyl chains displays a hexagonal columnar phase (Dh) between 88 and 108 °C. Columnar mesophases are also exhibited by benzamide dimers [138]. 

Fig. 1.1.10. Mesophases of discotic polymers (a) the hexagonal columnar phase. The diagram illustrates intercolumnar binding as well as intracolumnar back-folding of the main chain (Herrmann-Schonherr, Wendorff and Ringsdorf ) (b) the sanidic nematic phase composed of boards stacked parallel to one another (Herrmann-Schonherr et a/. ) (c) the columnar nematic phase (Ringsdorf...

DLCs generally exhibit two types of phases nematic phase and columnar phase (Fig. 7.1). Discotic nematic phases are rarely observed while columnar phases are commonly found. In the nematic phase, the molecules possess only orientational ordering however in the columnar phase, the disc-like molecules spontaneously self-assemble into infinite one dimensional (ID) stacks, which in turn self-organize to various two dimensional (2D) liquid crystalline lattices. The hexagonal columnar phase is the most commonly encountered phase in DLCs. Some discotic compounds are also known to exhibit lamellar and cubic phases. 

G glassy state, Dl discotic lamella phase, Nd discotic nematic phase, Colhi hexagonal columnar phase, I isotropic phase... 

Discotic architectures that use a central triphenylene core with six peripheral triphenylene units also exhibit colunmar mesophases, and these are commonly called star-like liquid crystals. Compoimd 28 is a very large molecule that uses flexible spacers to attach peripheral triphenylene units to a central discotic core in a star-like manner. The hexagonal columnar phase of compound 28 has been identified as hexagonal. Such stractmes are ohgomeric and could almost be considered polymeric (see Chapter 5). 

Figure 33. Mesophases of discotic polymers (a) hexagonal columnar phase (b) the board-like, or sanidic, nematic phase (c) the columnar nematic phase.

Fig. 2.13 Intra-columnar mobility in the hexagonal columnar phases (Db) of various discotic materials. The n indicates the number of carbon atoms in a discotic core of the materials. The mobility was determined by pulsed radiolysis transient microwave conductivity (PR-TRMC) measurements...

The discotic mesophases are classified in two types columnar, and nematic discotic. The structure of the nematic discotic mesophase (Np, Figure 8.3, left) is similar to that of rod-like molecules, but constituted by disk-like units. In columnar mesophases, the molecules are stacked in a columnar disposition and, depending on the type of columnar arrangement, several columnar mesophases are known. The most common lattices of the columnar phases are nematic discotic (No), columnar nematic (Ncoi), columnar hexagonal (Coin), and columnar rectangular (Col,) mesophases. 

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... 

Frenkel [412] also examined the behaviour of systems consisting of hard spheres in which the top and bottom have been cut off to form disclike structures. Here it is possible to demonstrate the existence of both discotic nematic and hexagonal columnar discotic phases. 

In discotic phases the orientation of the molecules is perpendicular to the molecular plane. Here, the columns can be arranged in a nematic or columnar manner. In the nematic phase the molecules possess a centre of gravity randomly ordered, but with the short molecular axis of each molecule more or less parallel. In the columnar phase, beside the preferable orientation of the short molecular axes, the disc-like molecules are ordered forming columns. Depending on the correlation strength between he columns these phases can be subdivided into ordered or disordered. A third possibility is to have a thermodynamically preferable position of the columns in the mesophase, like in a hexagonal cell. Additionally, a tilt of the columns is also possible. 

A few words of clarification about the nomenclature are relevant here. Columnar phases have been known for many years they were evident, for example, in the work of Spegt and Skoulios (28) on metal soaps, although these are not classical disk-shaped molecules. In 1977, however, a hexasubstituted benzene derivative was reported (29), this derivative was the first example of a properly disk-like mesogen, and the term discotic was coined to describe the mesophases it formed. Thus, for example, the discotic hexagonal phase was labeled Dh- The introduction of this nomenclature has actually caused confusion as disk-like molecules are not alone in their capacity to form columnar phases (indeed, some... 

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. 

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