Columnar mesophase liquid crystals

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.

Fig. 2.2 Typical liquid crysUilline molecules and their self-oiganized aggregates. Rod-like molecules form (a) the nematic phase and/or (b) smectic mesophases. Liquid crystal molecules orient in a given direction but have no positional order in the nematic phase, and they are arranged in layers in the smectic phases. Disc-hke molecules form (c) the nematic phase and (d) ate self-organized into columns in the columnar phases...

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... 

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. 

Several mixtures of hexanethiol capped gold nanopartides and triphenylene based discotic LCs have been studied. These mixtures display liquid crystal behavior (columnar mesophases) and an enhancement in the DC conductivity, due to the inclusion of gold nanoparticies into the matrix of the organic LC [70]. Other studies of mixtures of gold nanoparticies with mesogens indude a series of cholesteryl phenoxy alkanoates. The inclusion of the nanopartides does not change the inherent liquid crystal properties of the cholesteryl derivative but the mesophases are thermally stabilized [71]. 

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). 

Keywords Columnar mesophase Cubic mesophase Dendrimer Liquid crystal Metallomesogen Micro-segregation Organic semiconductor Perfluorinated molecule Polyphilic molecule Self-assembly... 

Depending on temperature, transitions between distinct types of LC phases can occur.3 All transitions between various liquid crystal phases with 0D, ID, or 2D periodicity (nematic, smectic, and columnar phases) and between these liquid crystal phases and the isotropic liquid state are reversible with nearly no hysteresis. However, due to the kinetic nature of crystallization, strong hysteresis can occur for the transition to solid crystalline phases (overcooling), which allows liquid crystal phases to be observed below the melting point, and these phases are termed monotropic (monotropic phases are shown in parenthesis). Some overcooling could also be found for mesophases with 3D order, namely cubic phases. The order-disorder transition from the liquid crystalline phases to the isotropic liquid state (assigned as clearing temperature) is used as a measure of the stability of the LC phase considered.4... 

Cobalt(II) nitrate induces a columnar nematic phase in the 1 2 complex with 98 (Table 7) as deduced from X-ray scattering which is stable for 30 K. Also, nickel(II) nitrate turned 98 into a liquid crystal with an unknown phase. The complex between 99 and copper(II) nitrate showed the same unknown mesophase. The phase range was 140 K but the samples decompose before clearing. A possible reason for the induction of a mesophase by complexation is the stiffening of the crown and the adjacent flexibly linked groups [112]. 

He and Cammidge prepared liquid crystal 113 (Scheme 59) with a central [27] crown-9 moiety, three attached triphenylene units carrying a total of 12 hexyloxy chains and exhibiting a columnar hexagonal mesophase [122]. 

The most comprehensive studies on shape-persistent Hekates have been performed on stilbenoid star-shaped molecules. Structures and mesomorphic properties are collected in Table 1. Core building blocks with only one repeating unit per arm and one flexible chain 26a,b, 28a-d, 30a did not show any liquid crystal properties [56-58]. In the series of two chain derivatives 28e, 30b,c the formation of meso-phases depend on the core [57-59]. The electron deficient triazine and the dicyanopyridine building block induced obviously columnar mesophases. The pyridine derivative 30b showed only a crystalline phase [58]. In the series of nine chain stars 26c-g [60-62] and 28f-n [57], the compounds formed columnar phases depending on the chain length of the peripheral chains. Propyloxy chains are too short but hexyloxy and dodecyloxy chains are sufficient for the formation of liquid crystal phases by nanosegregation [60-62]. This can be rationalised by a dense... 

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