The Chiral Nematic State

The chiral nematic state, first observed in cholesteryl derivatives, was later detected in other chiral mesogens, and can also he induced hy adding small chiral molecules to a host nematic TCP. Chiral nematic LCPs have thus heen synthesized as side-chain polymers hy introducing a chiral unit in the tail moiety of mesogens or hy copolymerizing cholesterol-containing monomers with another potential mesogenic monomer. Examples [4] of these types are shown as structures (V) and (VI) ... 

Many cellulose derivatives form Hquid crystalline phases, both in solution (lyotropic mesophases) and in the melt (thermotropic mesophases). The first report (96) showed that aqueous solutions of 30% hydroxypropylceUulose [9004-64-2] (HPC) form lyotropic mesophases that display iridescent colors characteristic of the chiral nematic (cholesteric) state. The field has grown rapidly and has been reviewed from different perspectives (97—101). 

The major difference between the configuration of the OMI sandwich cell and other STN-LCDs is that the optical path difference (5 = And 1 pm) is much lower. There is no requirement for a significant pretilt (0 < 0 < 5°), the twist angle of the chiral nematic layer is lower (180°), the front polariser is parallel to the nematic director (a = 0°) and the polariser and analyser are crossed (P = 90°). The 180° twist gives rise to strong interference between the two elliptically polarised rays. If the optical path difference is small, e.g. 0.4 m, a bright, white, non-dispersive off-state is produced. The chiral nematic mixture should be of positive dielectric anisotropy, low birefringence and exhibit a low cell gap to pitch ratio dip 0.3). 

The pitch of the helix for compound 42 was found to be approximately 0.2-0.3 xm, thus the material selectively reflects visible light over a wide temperature range. Moreover, the pitch is relatively temperature insensitive thus the material can be used in large area non-absorbing polarizers, or in optical notch filters or reflectors. In addition, in the glassy state the helical macrostructure of the chiral nematic phases is retained, thus similar applications are possible. 

Like the other side-chain LCPs described in the previous section, these materials also oflfer the possibility of locking the chiral nematic phase into the glassy state by rapid cooling to temperatures below Tg. This leads to a preservation of the structure and its reflected color. With suitable systems, the process can thus be used to produce stable and light-fast monochromatic films. 

Various models proposed may not account for all these experimental facts. The Keating [20] and Bottcher [21] evaluation does not account for such a variety of behavior. Goossens [22] proposed the chiral nematic structure as the result of an anisotropic dispersion energy between chiral mesogens, and predicts for thermotropic LCs a pitch that is essentially independent of temperature. Lin-Liu et al. [23] developed a theory that accounts for all the above-stated temperature effects. The temperature dependence of the pitch is determined by the shape and position of the intermolecular potential as a function of the intermolecular twist... 

A statistical model was introduced by Ki-mura et al. [25] which included attractive and repulsive asymmetric intermolecular forces for rod-like molecules. The results are summarized as Eq. (5), which is widely used for the lyotropic chiral nematic state... 

The phototuning of BPs can also be fabricated in a pure material system [147]. Das et al. reported a light-induced stable blue phase in photoresponsive diphen-ylbutadiene based mesogen 37. This compound was found to exhibit SmA and N during heating. When the temperature was kept at 118 °C, the photoisomerization induced an isothermal phase transition from SmA to N. Photoirradiation of the SmA film held at a higher temperature (124 °C) for 100 s resulted in transition to a phase with a characteristic classical BP texture showing in Fig. 5.30. The BP was thermodynamically stable and could be maintained at this state for several hours. The characteristic sharp reflection bands compared to the rather broad reflection bands observed for the chiral nematic phase confirmed the formation of BP. The photoinduced formation of the BP exhibited a reflection centered at 510 nm. Subsequent irradiation led to the blue shift to 480 nm in the reflection band. 

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