Chiral smectic materials

The ease of forming the smectic mesophase by this class of side-group type liquid crystalline polymers has rendered a great possibility in synthesizing polymeric chiral smectic materials useful in non-linear optics, transducers, pyroelectric detectors and display devices (Chapter 6). The first polymer forming a chiral smectic-C phase was synthesized by Shibaev et al. (1984). It has a polymethacrylate main chain, a long polymethylene spacer, and a mesogenic unit attached at the end with a chiral moiety (polymer (3.60)). Since then, a lot of polymers with chiral mesophases have been synthesized and studied (Le Barny and Dubois, 1989). 

The materials development is far from finished in the case of chiral smectic materials. The observation of highest importance for smectic C materials now relates to the property of a negative layer expansion coefficient 8j. In order to significantly increase the useful temperature range for high performance FLC displays, especially the lower end (for shipping by air a SmC phase stable down to -40 °C is desirable) we have to increase the available pool of molecular structures with this property of negative 7. This is an important task for synthetic chemists. 

Tbe purpose of tbe bydroxyl group is to acbieve some hydrogen bonding with the nearby carbonyl group and therefore hinder the motion of the chiral center. Another way to achieve the chiral smectic Cphase is to add a chiral dopant to a smectic Chquid crystal. In order to achieve a material with fast switching times, a chiral compound with high spontaneous polarization is sometimes added to a mixture of low viscosity achiral smectic C compounds. These dopants sometimes possess Hquid crystal phases in pure form and sometimes do not. 

The earliest approach to explain tubule formation was developed by de Gen-nes.168 He pointed out that, in a bilayer membrane of chiral molecules in the Lp/ phase, symmetry allows the material to have a net electric dipole moment in the bilayer plane, like a chiral smectic-C liquid crystal.169 In other words, the material is ferroelectric, with a spontaneous electrostatic polarization P per unit area in the bilayer plane, perpendicular to the axis of molecular tilt. (Note that this argument depends on the chirality of the molecules, but it does not depend on the chiral elastic properties of the membrane. For that reason, we discuss it in this section, rather than with the chiral elastic models in the following sections.)... 

Note 6 Chiral materials form chiral smectic F mesophases denoted by SmF. ... 

It can be safely predicted that applications of liquid crystals will expand in the future to more and more sophisticated areas of electronics. Potential applications of ferroelectric liquid crystals (e.g. fast shutters, complex multiplexed displays) are particularly exciting. The only LC that can show ferroelectric property is the chiral smectic C. Viable ferroelectric displays have however not yet materialized. Antifer-roelectric phases may also have good potential in display applications. Supertwisted nematic displays of twist artgles of around 240° and materials with low viscosity which respond relatively fast, have found considerable application. Another development is the polymer dispersed liquid crystal display in which small nematic droplets ( 2 gm in diameter) are formed in a polymer matrix. Liquid crystalline elastomers with novel physical properties would have many applications. 

The role of supramolecular chemistry in materials is perhaps expressed most impressively in liquid crystals, in which slight variations of chiral content can lead to dramatic influences in the properties of the mesophases. The helical sense of these mesophases is determined not only by intrinsically chiral mesogens but also by the use of dopants which more often than not interact with achiral host LCs to generate chiral phases (Fig. 7). These phenomena are important both scientifically and technologically, most notably for the chiral smectic and cholesteric liquid crystal phases [68-71]. These materials—as small molecules and as polymers [72,73]—are useful because their order... 

In general, cholesteric liquid crystals are found in optically active (chiral) mesogenic materials. Nematic liquid crystals containing optically active compounds show cholesteric liquid crystalline behavior. Mixtures of right-handed and left-handed cholesteric liquid crystals at an adequate proportion give nematic liquid crystals. From these results cholesteric liquid crystals are sometimes classified into nematic liquid crystals as twisted nematics . On the other hand, cholesteric liquid crystals form batonnet and terrace-like droplets on cooling from isotropic liquids. These behaviors are characteristic of smectic liquid crystals. Furthermore, cholesteric liquid crystals correspond to optically negative mono-axial crystals, different from nematic... 

Calamitic metallomesogens forming a chiral smectic C phase (SmC ) are ferroelectric materials. Due to the low symmetry of this phase when the helix is unwound (C2) the molecular dipoles are aUgned within the layers of the SmC phase, giving rise to ferroelectric order in the layers. Because the SmC phase has a helical structure, there is no net macroscopic dipole moment for the bulk phase. However, it is possible to unwind the helix by application of an external electric field or by surface anchoring in thin cells. Under such conditions, a well-aligned film of the ferroelectric liquid crystal can exhibit a net polarisation, called the spontaneous polarisation (Ps). Ferroelectric liquid crystals are of interest for display applications because the macroscopic polarisation can be switched very fast by an... 

Chirality is also an important aspect of liquid crystals. The introduction of chiral moieties into the chiral smectic phases induces functions such as ferroelectricity and antiferroelectricity. A few of the unconventional chiral liquid crystals are described in Chapter 1. The blue phase is one of the exotic chiral liquid crystalline phases. In Chapter 3, Kikuchi introduces the basic aspects and recent progress in research of the blue phase. Recently, the materials exhibiting the blue phases have attracted attention because significant photonic and electro-optic functions are expected from the materials. 

The structure of the smectic A phase when it is composed of optically active material (i.e., smectic A ) remains the same as that for the achiral phase. The molecules are arranged in diffuse disordered layers, and there is no long-range periodic order. However, because of the molecular chirality, the environmental symmetry is reduced to [10]. As a consequence, when an electric field is applied to a chiral smectic A= phase there will be a coupling of the electroclinic susceptibility to the field and the long axes of the molecules will tilt with respect to the layer planes. The tilt angle, for relatively low applied fields, varies linearly with the field. This linear electrooptic phenomenon is called the electroclinic effect. 

Since the synthesis of the first chiral smectic C side chain LCP by Shibaev et al. [6], chemists over the last ten years have considerably extended that field. Now, the SmC mesophase can be exhibited by a variety of polymeric materials including homopolymers, copolymers and terpolymers, oligomers, combined polymers, and cross-linked polymers. 

Chiral smectic ferroelectric liquid crystals are liquids that possess spontaneous polar order. Combined with their excellent processibility on silicon integrated circuits, these liquid crystals provide an attractive potential approach to synthesis of materials for second order nonlinear optics, provided adequate second order susceptibility can be obtained. Unfortunately, the second-order nonlinear optical susceptibility of the ferroelectric liquid crystals are usually low and their thermal stability is limited. Several, very interesting approaches to utilization of liquid crystals, however, were carried out. 

More recently, it has been theoretically predicted by Brand [81] that elastomeric networks that have chiral nematic or smectic C mesophases should have piezoelectric properties. The non-centro-symmetric material responds to the deformation via a piezoelectric response. Following this prediction, both Finkelmann and Zental have reported the observation of piezoelectricity. In one case, a nematic network was converted to the cholesteric form with the addition of CB15, 2 -(2-methylbutyl)biphenyl-4-carbonitrile [82]. By producing a monodomain, it is possible to measure the electro-mechanical or piezoelectric response. Compression leads to a piezoelectric coefficient parallel to the helical axis. Elongation leads to the perpendicular piezoelectric response. As another example, a network with a chiral smectic C phase that possesses ferroelectric properties can also act as a piezoelectric element [83]. Larger values of this response might be observed if crosslinked in the Sc state. 

In the first illustration of the combined DoM-cross-coupling-DreM sequence in material science, rod-shaped chiral mesogens, 247 and 248, have been synthesized, 244—r 245 —r 246 (Scheme 14.47), and shown to display chiral smectic phase C ... 

Chiral smectic C materials have mostly been designed to have a high Pg and a low viscosity to enable their use in ferroelectric devices. The stracture of chiral smectic C materials is sirmmarised by a template structure in Figure 6.4 which also shows the types of moieties and their combination. The first S material used to establish the viability of a device was DOBAMBC (7a) in 1974. The use of ester and ether moieties provides the necessary lateral dipoles for molecular tilting and the use of the conjugated cinnamate... 

In recent years chirality in liquid crystals has developed into a very important area of liquid crystal research. Chiral materials are reqtrired for the chiral nematic (N ) phase and the ferroelectric chiral smectic C (S ) phase for a wide variety of applicatiorrs. As... 

---