Helicity chiral nematics

Figure C2.2.2. Isotropic, nematic and chiral nematic phases. Here n denotes tire director. In tire chiral nematic phase, tire director undergoes a helical rotation, as schematically indicated by its reorientation around a cone.

Other more exotic types of calamitic liquid crystal molecules include those having chiral components. This molecular modification leads to the formation of chiral nematic phases in which the director adopts a natural helical twist which may range from sub-micron to macroscopic length scales. Chirality coupled with smectic ordering may also lead to the formation of ferroelectric phases [20]. 

Here, ry is the separation between the molecules resolved along the helix axis and is the angle between an appropriate molecular axis in the two chiral molecules. For this system the C axis closest to the symmetry axes of the constituent Gay-Berne molecules is used. In the chiral nematic phase G2(r ) is periodic with a periodicity equal to half the pitch of the helix. For this system, like that with a point chiral centre, the pitch of the helix is approximately twice the dimensions of the simulation box. This clearly shows the influence of the periodic boundary conditions on the structure of the phase formed [74]. As we would expect simulations using the atropisomer with the opposite helicity simply reverses the sense of the helix. 

When the mesogenic compounds are chiral (or when chiral molecules are added as dopants) chiral mesophases can be produced, characterized by helical ordering of the constituent molecules in the mesophase. The chiral nematic phase is also called cholesteric, taken from its first observation in a cholesteryl derivative more than one century ago. These chiral structures have reduced symmetry, which can lead to a variety of interesting physical properties such as thermocromism, ferroelectricity, and so on. 

The introduction of a second chiral atom in the system leads to a reduction in the mesogenic properties and only a monotropic chiral nematic transition is observed for compound 23. However, when this compound is cooled down from the isotropic liquid state at a cooling rate of 0.5 °Cmin , very unusual blue phases BP-III, BL-II and BP-I are observed in the range 103-88 °C. Blue phases usually require pitch values below 500 nm. Hence the pitch value of the cholesteric phase for 23 must be very short, suggesting that the packing of two chiral carbons forces a faster helical shift for successive molecules packed along the perpendicular to the director. 

In particular most of the early studies on CPL were based on the incorporation of a luminescent achiral chromophore in a chiral nematic or cholesteric liquid crystal. Chiral nematic liquid crystals (CNLC) are intrinsically birefringent and exhibit a helical supramo-lecular architecture, which is characterized by the pitch length p (Figure 5.11). 

FIGURE 5.11 Supramolecular, helical architecture and definition of pitch length p of chiral nematic liquid crystals. 

The chiral nematic assembly is formed by materials that have chiral centers and that form a nematic phase. Here, a chiral-imposed twist is imparted to the linear chains composing each layer, resulting in a three-dimensional helical arrangement. 

If the molecules of a liquid crystal are optically active Ichiral), then the nematic phase is not formed. Instead of the director being locally constant as is the case for nematics, the director rotates in helical fashion throughout the sample, Within any plane perpendicular to the helical axis the order is nematic-like. In other words, as in a nematic there is only orienlalional order in chiral nematic liquid crystals, and no positional order. 

Subsequent studies on the chiral nematic phase of 8 and 10 showed the influence of complexed salts on the liquid crystalline properties. In the complexes (Scheme 5), the helical pitch was strongly affected by the complexed cation and the counterions [29]. 

Crown ether binaphthyl derivatives 128-131 (Scheme 71) were synthesized and investigated by Akagi [139], Compounds 128-131 were used to induce chiral nematic phases (N ) in liquid crystals. It was found that the helical twisting power increased with decreasing ring size. Helical polyacetylenes were synthesized in the N phases. It was found that the interdistance between the fibril bundles of the helical polyacetylene was equal to the half-helical pitch of the N liquid... 

A cholesteric, or chiral nematic (N ) phase. This is a positionally disordered fluid in which the constituent molecules align on average their axes along a common direction called the nematic director. Being the DNA helices chiral, the orientational order develops an additional macro-helical superstructure with the twist axis perpendicular to the local director. The phase thus consists of local nematic layers continuously twisted with respect to each other, with periodicity p/2 (where p is the cholesteric pitch see Fig. 8a) [27,28]. For 150-bp helices, the N phase appears at a concentration around 150 mg/mL in 100 mM monovalent salt conditions. This LC phase is easily observed in polarized optical microscopy. Since the N pitch extends to tens of micrometers (that is, across... 

Finally, dispersions of MWCNT in chiral nematic liquid crystals were studied as well. These experiments suggested no change in the helical twisting characteristics of the chiral nematic phase. However, the MWCNTs were thought to disrupt the translational order in the SmA phase (decrease of the SmA-N phase transition) yet follow the twist of the nematic director in the chiral nematic phase [498]. 

A. di Matteo, S. M. Todd, G. GottareUi, G. Solladie, V. E. Williams and R. P. Lemieux, Correlation between molecular structure and helicity of induced chiral nematics in terms of short-range and electrostatic-induction interactions. The case of chiral biphenyls, J. Am. Chem. Soc., 123 (2001) 7842-7851. 

Figure 2.3 Schematic representation of the periodical helical structures of the chiral nematic (cholesteric) phase. The pitch of the helix corresponds to the rotation of the director through 360°. There is no layered structure in a chiral nematic. N. phase.

When the helix is completely unwound a clear state is produced as a consequence of the formation of a pseudonematic phase with no helical structure from the corresponding chiral nematic phase. The analyser then absorbs linearly polarised light. Therefore, black information can be displayed at the appropriate pixels against a white background to produce an image with positive contrast. The threshold voltage for the unwinding of the helix is dependent on a number of physical parameters ... 

The application of an electric field above the threshold value results in a reorientation of the nematic liquid crystal mixture, if the nematic phase is of negative dielectric anisotropy. The optically active dopant then applies a torque to the nematic phase and causes a helical structure to be formed in the plane of the display. The guest dye molecules are also reoriented and, therefore, the display appears coloured in the activated pixels. Thus, a positive contrast display is produced of coloured information against a white background. The threshold voltage is dependent upon the elastic constants, the magnitude of the dielectric anisotropy, and the ratio of the cell gap to the chiral nematic pitch ... 

Molecules that contain a chiral center can form chiral liquid crystalline phases, where the orientation direction rotates in a helical fashion as one moves along the helical axis, which is perpendicular to the locally preferred direction of orientation. Both nematic and smectic phases can be chiral. In a chiral nematic phase, also known as a cholesteric, as one moves along the helical axis, the director rotates sinusoidally (see Fig. 10-31. Thus, if z is... 

As another example of a helical polyacetylene, the single-handed helical polyacetylene fibril, whose structure was studied by SEM, was prepared by the polymerization of acetylene within a chiral nematic liquid crystalline phase.192... 

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