Cholesteric phase optical properties

P-chiral dibenzophosphole oxide (52a) (Scheme 14) shows liquid crystalline behaviour [52], a property that is of interest in the area of electro-optical displays [53]. Chiral resolution of (52a) was achieved by column chromatographic separation of the diastereoisomers obtained following coordination of the o -benzophosphole (52b) to chiral cyclometallated palladium(II) complexes [52]. Notably, the presence of a stereogenic P-centre is sufficient to generate a chiral cholesteric phase. 

Obviously, chirality is an essential property in molecular chemistry, and knots are exciting systems in this context. With a touch of fantasy, it could be conceived that some of the chemical processes for which chirality is essential (enan-tioselection of substrates, asymmetric induction and catalysis, cholesteric phases, and ferroelectric liquid crystals molecular materials for non linear optics...) could one day use enantiomerically pure knots. 

The systematic synthesis of non amphiphilic l.c.-side chain polymers and detailed physico-chemical investigations are discussed. The phase behavior and structure ofnematic, cholesteric and smectic polymers are described. Their optical properties and the state of order of cholesteric and nematic polymers are analysed in comparison to conventional low molar mass liquid crystals. The phase transition into the glassy state and optical characterization of the anisotropic glasses having liquid crystalline structures are examined. 

The realization of nematic side chain polymers implies the possibility of the existence of cholesteric side chain polymers, presuming the mesogenic molecules, which are linked to the backbone, are chiral. For these polymers it is of interest, whether the polymer fixation influences the helical twist and therefore the optical properties of the cholesteric phase. This will be discussed in 2.3.2.2. 

The macromolecular nature provides an interesting feature of LC polymeric cholesterics, namely the possibility of obtaining monochromic films. Thus for polymeric liquid crystals the helix pitch is practically not altered with temperature below Tg, when a cholesteric phase is frozen in a glassy matrix (Fig. 23a). This implies that fast cooling of polymeric films from a mesomorphic state (shown with arrows) fixes their optical properties, which makes it possible to use them at ordinary temperatures as selective monochromic reflectors. On the other hand, such polymeric films display the extraordinary polarizing properties of cholesterics, i.e. the different absorption... 

Liquid-crystalline solutions and melts of cellulosic polymers are often colored due to the selective reflection of visible fight, originating from the cholesteric helical periodicity. As a typical example, hydroxypropyl cellulose (HPC) is known to exhibit this optical property in aqueous solutions at polymer concentrations of 50-70 wt%. The aqueous solution system is also known to show an LCST-type of phase diagram and therefore becomes turbid at an elevated temperature [184]. 

Experimentally, the cholesteric structure parameters, i.e., pitch and handedness, can be derived from the optical properties of the phase and very specially from its so-called selective reflection. This most striking phenomenon is the reflection of one component of circular polarized radiation in a spectral interval around that wavelength which within the medium matches the cholesteric pitch, i.e. XrIh = i when n denotes the... 

Unfortunately, there is no report on the detailed physical characterization of these polymers. Such information as unidirectional twist angle and form optical rotation, as well as their dependence on chemical structures and temperature, can be very useful in further understanding the molecular orientations of the polymers in the cholesteric phase. In contrast, a number of studies have been made on the physical-chemical properties of cholesteric lyotropic polymer systems, especially polypeptides. 

However, there is a structure consistent with both the required space group and the optical properties. The gyroid surface, which occurs frequently in lipid-water systems, provides such a possibility. If we assume that cholesterol skeletons form rod-like infinite helices, this structure represents an effective three-dimensional packing of such helices. Thus, the rods form a body-centered arrangement as shown in Fig. 5.5. In this structure, there is a helical twist between the rods, in addition to the cholesteric twist within each rod. The h)rperbolic structure is a consequence of the chirality of the esters, which induces torsion into the packing arrangement. A racemic mixture does not exhibit this phase natural cholesteric esters contain a single enantiomer only. 

First X-ray measurements show that the helical superstructure of the cholesteric and chiral smectic C phase can be untwisted by stretching the elastomer (5). High strains of 300% are necessary for this purpose (compared to 20% for the achiral elastomers). Nevertheless these results show that the chiral lc elastomers have the potential to act as mechano-optical couplers (cholesteric phase) or as piezo-elements (chiral smectic C phase) (5), because the mechanically induced change of the helical superstructure has to change the optical transmission or reflection properties or the spontaneous polarization. Both effects however have not yet been measured directly. 

In this liquid crystal phase, the molecules have non-symmetrical carbon atoms and thus lose mirror symmetry. Otherwise optically active molecules are doped into host nematogenic molecules to induce the chiral liquid crystals. The liquid crystals consisting of such molecules show a helical structure. The most important chiral liquid crystal is the cholesteric liquid crystals. As discussed in Section 1.2, the cholesteric liquid crystal was the first discovered liquid crystal and is an important member of the liquid crystal family. In some of the literature, it is denoted as the N phase, the chiral nematic liquid crystal. As a convention, the asterisk is used in the nomenclature of liquid crystals to mean the chiral phase. Cholesteric liquid crystals have beautiful and interesting optical properties, e.g., the selective reflection of circularly polarized light, significant optical rotation, circular dichroism, etc. 

Display devices can also be constructed using the field effect, the cholesteric memory effect and the cholesteric-nematic phase change effect [259, 262]. The recognition of the useful electro-optical properties of liquid crystals has stimulated efforts in synthesis of new mesomorphic materials. Today, more than 6000 compounds are available but an ideal liquid crystal is still elusive. 

The nematic phase (N, ) is exhibited by relatively few compounds examples are hexakis((4-octylphenyl)ethynyl)benzene (fig. 6.1.1(A)) and the hexa-n-alkyl and alkoxybenzoates of triphenylene (fig. 6.1.1(e)). The Nd phase has an orientationally ordered arrangement of the discs with no long-range translational order (fig. 6.1.2(f)). Unlike the usual nematic of rod-like molecules, is optically negative, the director n now representing the preferred axis of orientation of the disc normal. The properties of this phase will be discussed in greater detail in 6.5. A twisted nematic (or cholesteric) phase, with the helical axis normal to the director, has also been identified. ... 

Many cellulose derivatives form lyotropic liquid crystals in suitable solvents and several thermotropic cellulose derivatives have been reported (1-3) Cellulosic liquid crystalline systems reported prior to early 1982 have been tabulated (1). Since then, some new substituted cellulosic derivatives which form thermotropic cholesteric phases have been prepared (4), and much effort has been devoted to investigating the previously-reported systems. Anisotropic solutions of cellulose acetate and triacetate in tri-fluoroacetic acid have attracted the attention of several groups. Chiroptical properties (5,6), refractive index (7), phase boundaries (8), nuclear magnetic resonance spectra (9,10) and differential scanning calorimetry (11,12) have been reported for this system. However, trifluoroacetic acid causes degradation of cellulosic polymers this calls into question some of the physical measurements on these mesophases, because time is required for the mesophase solutions to achieve their equilibrium order. Mixtures of trifluoroacetic acid with chlorinated solvents have been employed to minimize this problem (13), and anisotropic solutions of cellulose acetate and triacetate in other solvents have been examined (14,15). The mesophase formed by (hydroxypropyl)cellulose (HPC) in water (16) is stable and easy to handle, and has thus attracted further attention (10,11,17-19), as has the thermotropic mesophase of HPC (20). Detailed studies of mesophase formation and chain rigidity for HPC in dimethyl acetamide (21) and for the benzoic acid ester of HPC in acetone and benzene (22) have been published. Anisotropic solutions of methylol cellulose in dimethyl sulfoxide (23) and of cellulose in dimethyl acetamide/ LiCl (24) were reported. Cellulose tricarbanilate in methyl ethyl ketone forms a liquid crystalline solution (25) with optical properties which are quite distinct from those of previously reported cholesteric cellulosic mesophases (26). 

Today we know that the cholesterol esters crmsist of helical (chiral) molecules, and on cooling from the isotropic phase they rmdergo a transition into another phase called a cholesteric phase. This shows unique optical properties. In Fig. 1.3a we see a photo-image of a 20 pm thick polycrystalline layer of cholesteryl acetate viewed in a polarizing microscope. Upon heating the substance melts, that is it becomes... 

A cholesteric forms a helical structure and its optical properties are characterised by the tensor of dielectric permittivity rotating in space. We are already familiar with the form of the cholesteric tensor (see Section 4.7). It was Oseen [1] who suggested the first quantitative model of the helical cholesteric phase as a periodic medium with local anisotropy and very specific optical properties. First we shall discuss more carefully the Bragg reflection from the so-called cholesteric planes . 

Fig. 16 Optical properties of different lyotropic cholesteric phases of cellulose carbanilates,...

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