Liquid discotic

A particular attribute of octasubstituted phthalocyanines is their liquid crystalline behavior. Phthalocyanines substituted in peripheral positions by long-chain substituents form, depending on the structure (alkyl or alkoxy), liquid discotic (from the disclike shape of the molecules) crystalline phases [68-71 ] or columnar meso-phases [72]. Liquid crystalline phases are found for side chains longer than C4 or Q (depending on the metals and substituents used) [73]. In these mesophases the phthalocyanine moieties stack in columns with arrangements of different symmetry (Fig. 15.8), depending on the nature of the side chains [71,74]. Only chains connected with a heteroatom X (X = O, S) to the aromatic macrocycle show an arrangement with the molecular planes perpendicular to the column axis. 

A particular attribute of octasubstituted phthalocyanines is their liquid crystalline behavior. Phthalocyanines substituted in peripheral positions by long chain substituents form, depending upon the structure (alkyl or alkoxy), liquid discotic (from the disc-like shape of... 

Thennotropic liquid crystal phases are fonned by anisotropic molecules witli long-range orientational order and in many types of stmcture witli some degree of translational order. The main types of mesogen are Arose tlrat are rodlike or calamitic and Arose Arat are disclike or discotic. 

Figure C2.2.7. Schematic illustrating tire classification and nomenclature of discotic liquid crystal phases. For tire columnar phases, tire subscripts are usually used in combination witli each otlier. For example, denotes a rectangular lattice of columns in which tire molecules are stacked in a disordered manner (after [33])...

Thennotropic liquid crystal phases are fonned by rodlike or disclike molecules. However, in the following we consider orientational ordering of rodlike molecules for definiteness, although the same parameters can be used for discotics. In a liquid crystal phase, the anisotropic molecules tend to point along the same direction. This is known as the director, which is a unit vector denoted n. 

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. 

Discotic blue phases Discotic liquid crystals Discover Disc Tube... 

Liquid crystals may be divided into two broad categories, thermotropic and lyotropic, according to the principal means of breaking down the complete order of the soHd state. Thermotropic Hquid crystals result from the melting of mesogenic soHds due to an increase in temperature. Both pure substances and mixtures form thermotropic Hquid crystals. In order for a mixture to be a thermotropic Hquid crystal, the different components must be completely miscible. Table 1 contains a few examples of the many Hquid crystal forming compounds (2). Much more is known about calamitic (rod-Hke) Hquid crystals then discotic (disk-like) Hquid crystals, since the latter were discovered only recendy. Therefore, most of this section deals exclusively with calamities, with brief coverage of discotics at the end. 

Fig. 12. Molecular structure and phases of a typical discotic liquid crystal.

A relatively new class of high-performance carbon fibers is melt-spun from mesophase pitch, a discotic nematic liquid crystalline material. This variety of carbon fibers is unique in that it can develop extended graphitic crystallinity during carbonization, in contrast to current carbon fibers produced from PAN. 

The rigid nature of the mesophase pitch molecules creates a strong relationship between flow and orientation. In this regard, mesophase pitch may be considered to be a discotic nematic liquid crystal. The flow behavior of liquid crystals of the nematic type has been described by a continuum theory proposed by Leslie [36] and Ericksen [37]. 

The reaction was extended to PhCH2X (X = Cl or Br) which gives the hexa(phenyl-ethyl)benzene complex. The new free aromatic ligand is easily disengaged by photolysis in acetonitrile [76a] Eq. (20). This line of research is now offering us the perspective of making new discotic liquid crystals using suitably substituted... 

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]. 

There have been several simulations of discotic liquid crystals based on hard ellipsoids [41], infinitely thin platelets [59, 60] and cut-spheres [40]. The Gay-Berne potential model was then used to simulate the behaviour of discotic systems by Emerson et al. [16] in order to introduce anisotropic attractive forces. In this model the scaled and shifted separation R (see Eq. 5) was given by... 

To date, the crystal structures of more than 200 mesogenic compounds are known. In this review, we wish to present a general overview of the crystal structures of mesogenic compounds up to the end of 1997. Unfortunately, it is not possible to consider the crystal structure determinations of carbohydrate liquid crystals [13, 14], metallomesogens [15-18], phasmid and biforked mesogens [19-22], perfluorinated mesogenic compounds [23-27], benzoic acids [6, 28-31], cinnamic acids [7, 32, 33], dicarboxylic acids [34, 35], cinnamate compounds [8, 36-40], and discotic liquid crystals [41-43] due to the lack of space. 

It is not possible to predict from the related crystal structure alone whether the compound will melt to a liquid crystalline phase or not, because the anisotropic molecules (calamitic and discotic ones) form in favourable anisotropic packing. As a rule long shaped rod-like molecules quite often possess a layered arrangement in the solid state regardless of whether the compound is mesogenic or not. 

Since the discovery of discotic liquid crystals [121], the mesophases formed by rod-like and disc-like molecules have been considered as belonging to different liquid crystalline classes. Indeed, the conventional rod-like and disc-... 

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 crystals (LCs) are organic liquids with long-range ordered structures. They have anisotropic optical and physical behaviors and are similar to crystal in electric field. They can be characterized by the long-range order of their molecular orientation. According to the shape and molecular direction, LCs can be sorted as four types nematic LC, smectic LC, cholesteric LC, and discotic LC, and their ideal models are shown in Fig. 23 [52,55]. 

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]. 

Coco, S Espinet, P Marb n-Alvarez, J.M. and Levelut, A.M. (1997) Effects of Isonitrile Substituents on Mesogenic Properties of Halogoldiisonitrile Complexes Calamitic and Discotic Liquid Crystals. Journal of Materials Chemistry, 7, 19-23. 

Yamada, M., Shen, Z. and Miyake, M. (2006) Self-assembly of discotic liquid crystalline molecule-modified gold nanopartides control of ID and hexagonal ordering induced by solvent polarity. Chemical Communications, (24), 2569-2571. 

The interest in the structures of simple R2Si(OH)2 compounds lies in the fact that one of them, Bu 2Si(OH)2, forms a discotic liquid crystalline phase (308,309). Despite many attempts, it has not proved possible to obtain crystals of Bu 2Si(OH)2 suitable for a crystallographic study, the material obtained from various solvents usually being of a fine fibrous nature. The discotic phase of Bu 2Si(OH)2 has been proposed (309) to be due to the formation of dimeric disks of molecules which remain on breaking the interdimer hydrogen bonds in a structure of type 65 at the transition between crystal and mesophase. As has been described, structure type 65 is found for several diols similar to Bu 2Si(OH)2, and it is thus quite likely that Bu 2Si(OH)2 does indeed have the proposed structure. 

There are now three major shape classifications of low molar mass liquid crystals - rod-like (calamitic), disc-like (discotic) and bent-core. The last of these is the most recent, and while examples of bent mesogens have been known for some years, it is only since the mid-1990s that the area has attracted widespread attention [2],... 

Discotic liquid crystals on the other hand are based around a fairly flat core structure and are generally surrounded by six or eight peripheral alkyl(oxy) chains. Examples are given in Fig. 3. 

Considerably less work has been done on discotic liquid-crystalline elastomers [189,190] and cholesteric elastomers [191]. The same seems to be true for smectic elastomers [192,193], even though some of them have the additional interesting property of being chiral [194,195]. 

Chiral Lyotropic Discotic Liquid Crystals and Self-Assembly of Chiral Discotics in Dilute Solution... 

It was quickly recognized that chirality would play an important role in discotic liquid crystals, not only for the possibility of creating cholesteric and ferroelectric liquid crystals but also as a tool for studying the self-assembly of these molecules as a whole, both in solution and in the solid state. However, initial studies revealed that expression of chirality in discotic liquid crystals was not as straightforward as for liquid crystals derived from calamitic molecules. More recently, with the increase in interest in self-assembly and molecular recognition, considerably more attention has been directed to the study of chiral discotics and their assemblies in solution. The objective of this chapter is... 

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