Calamitic mesophases smectic

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. 

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). 

The mesophases of calamitic mesogens are classified in two groups nematic and smectic. The nematic mesophase (N) is characterized by an orientational order of the molecules that are aligned along a preferred direction (defined by a director n) (Figure 8.2). The molecules can slide and move in the nematic mesophase (while roughly keeping their molecular orientation) and rotate around their main axis. This is the less ordered mesophase and it is usually very fluid. 

Calamitic mesogens in general form two main types of mesophase the nematic phase (N) and the smectic (S) phases. The nematic phase is the most disordered of the mesophase tjpes in it, the molecules possess one-dimensional orientational order and no positional order (Fig. 22). 

Calamitic phases are essentially defined as a set of mesophases that occur between the breakdown of the long-range periodic, translational ordering of the crystal and the loss of long range orientational order at the transition to the isotropic liquid. In this context six mesophases exist the nematic phase and five smectic phases labelled A, B, C, F and I. Other closely related soft crystal phases, in which the molecules have long-range periodic order but are themselves rotationally disordered, also exist in concert with liquid crystal phases. This second set of mesophases are labelled E, J, G, H, and K, and are essentially the crystal versions of the... 

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... 

Figure 27. Snapshots of typical instantaneous configurations (left panel) and inherent structures (right panel) for the model calamitic system GB(3, 5, 2, 1) at various mesophases. From top to bottom isotropic phase, nematic phase, and smectic phase. (Reproduced from Ref. 131.)...

The true liquid-crystal mesophases of calamitic mesogens are divided into two classes—the nematic and smectic phases and these will be described in turn. There is, in addition, a series of crystal smectic phases that are not really liquid-crystal phases but which for many years were classified as such these will be mentioned briefly below. 

Similarly to the molecular engineering of calamitic molecules to produce ferroelectric smectic C phases [129], disk-like molecules with chiral peripheral chains tilted with respect to the columnar axis were predicted to lead to ferroelectric columnar mesophases [130]. Indeed, as it is the case with all flat disk-shaped mesogenic molecules, the tilt is mainly associated with the flat rigid aromatic cores of the molecules, the side-chains being in a disordered state around the columnar core. Thus, the nearest part of the chains from the cores makes an angle with the plane of the tilted aromatic part of the molecules. If the chiral centre and the dipole moment are located close to the core, then each column possesses a non-zero time averaged dipole moment, and therefore a spontaneous polarization. For reasons of symmetry, this polarization must be, on average, perpendicular to both the columnar axis and to the tilt direction in other words, the polarization is parallel to the axis about which the disk-shaped molecules rotate when they tilt as shown in Fig. 29. 

Whereas monophilic liquid crystals can show a high diversity of smectic phases (SmA-SmQ), the amphotropic liquid crystals normally exhibit only the SmA phase. Tilted smectic phases are only observed in a few cases. The first indication of possibly tilted phases was given in 1933 for thallium stearate [ 170]. A disordered SmC phase was also clearly deseribed for mesogens containing a classical calamitic core aside to their amphiphilic structure [171]. Monophilic liquid crystals can show various ordered tilted smectic phases, for example, smectic I, F, G, J, H, and K. In the case of lipids only one mesophase, the j8 phase,... 

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