Cholesteric twisted nematic

There are several related phenomena that will not be treated in this chapter. They include the well documented transformation of nematic phases into cholesteric (twisted nematic) phases by adding small amounts of optically active molecules to a nematogen [171], creation of smectic phases from mixtures of molecules which alone form only nematic phases [172,173], and the presence of reentrant phases [174] due to molecular reorganizations based upon the relative importances of various short- and long-range intermolecular interactions in different temperature regimes (as mediated by the interplay of entropy and enthalpy terms) [175 -177]. Each has been exploited to create interesting and novel systems and devices based upon mesomorphism. 

Figure 6.2 Discotic molecules in a (a) nematic state ND, (b) twisted nematic discotic state Np (P/2 is half of cholesteric pitch), (c) columnar state, ordered D0 and disordered Dd, (d) hexagonal ordered columnar state Dho two-dimensional packing arrays for columnar structures in (e) hexagonal, Colh rectangular, Colr oblique, Col0b.

Thermotropic cholesterics have several practical applications, some of which are very widespread. Most of the liquid crystal displays produced use either the twisted nematic (see Figure 7.3) or the supertwisted nematic electrooptical effects.6 The liquid crystal materials used in these cells contain a chiral component (effectively a cholesteric phase) which determines the twisting direction. Cholesteric LCs can also be used for storage displays utilizing the dynamic scattering mode.7 Short-pitch cholesterics with temperature-dependent selective reflection in the visible region show different colors at different temperatures and are used for popular digital thermometers.8... 

Research Focus Method for preparing polymerizable chiral intermediates containing optically active isosorbide to prepare twisted nematic or cholesteric phases. 

As the cholesteric phase is a twisted nematic phase, the orientational long range order of the mesogenic molecules, characterized by Eq. (3) ... 

That both phenomena arise as a consequence of macroscopic solvent order and not Intimate solvent-solute Interactions Is clear Saeva and 01In (75) have shown that solute LCICD spectra can be observed In twisted nematic phases only Nakazaki et al. (76) find an excess of one enantiomer of hexahelicene Is produced photochemlcally from achiral precursors In twisted nematic phases no LCICD spectra or optical Induction occurs In untwisted nematic phases and the handedness of the twist can be correlated with the sign of the LCICD and the preferred product enantiomer. Furthermore, Isotropic phases of cholesteric mixtures display no discernible LCICD spectra (12, 67) and the enantiomeric excesses In products of photolablle reactants In Isotropic phases are near zero (51). 

While the vast majority of studies on chiral induction were mainly concerned with the induction of the chiral (twisted) nematic or cholesteric phase, more recently induction of the smectic C phase in the smectic C has come to the fore, with a special emphasis on the way chirality is transferred between molecules [ 115]. It should also be noted that comparison of the chiral induction phenomena in the two types of LC phase and in other media can provide useful information concerning mechanisms of transfer and amplification of stereochemical information [116]. 

Fig. I. Schematic diagrams of the contrast versus the applied field for (a) a twisted nematic, (b) a cholesteric guest-host bistable display (Wysocki ei al., 1972 Ohtsuka and Sukamoto, 1973), and (c) a bistable LCD (Boyd et al., 1982).

Twisting a nematic structure around an axis perpendicular to the average orientation of the preferred molecular axes, one arrives at the molecular arrangement commonly called cholesteric (Kelker and Hatz, 1980). The twisted nematic phase is optically uniaxial, however with the axis perpendicular to the (rotating) director. Such a mesophase combines the basic properties of nematics with the implications of chirality The structure itself is chiral and as a consequence, a non-identical mirror image exists as it is shown schematically in Fig. 4.6-7. Besides the order parameters mentioned before, the essential characteristics of a cholesteric mesophase are the pitch, i.e., the period of the helical structure as measured along the twist axis, and its handedness, i.e., whether the phase is twisted clockwise or anticlockwise. 

Such twisted nematic phases are called induced cholesteric solutions and - as schematically outlined in Fig. 4.6-9 - enantiomers cause countercurrently twisted structures. As discussed by Korte and Schrader (1981) this effect offers the potential of sensitively characterizing the chirality of small amounts of optically active compounds. There are no restrictions as to the type of chirality, and the experiments can advantageously be based on infrared spectroscopy. The application of induced cholesteric solutions was later reviewed again by Solladie and Zimmermann (1984). The host phase is the more twisted the more of the optically active guest compound is dissolved. Quantifying the twist by the inverse pitch z and the concentration by the molar fraction x, the ability of a chiral. solute to twist a given nematic host phase is characterized by the helical twisting power (HTP Baessler and Labes, 1970). For small values of a this quantity P is defined by the relation... 

A lyotropic, nematic solution of cellulose was formed in a NH3/NH4SCN solvent in what are presumably good solvent compositions. Evidence strongly suggests that the twisted nematic or cholesteric structure that results when solutions of chiral cellulose chains interact may be repressed or compensated so that interactions among chiral centers are minimized. Our reasoning is based a body of experimental evidence which includes ... 

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... 

The cholesteric liquid, which is a spontaneously twisted nematic, behaves like a negative uniaxial crystal, so that light vibrating perpendicular to the molecular layers shows maximum velocity. Linearly polarized light transmitted perpendicular to the molecular layers shows rotation of its electrical vector along a helical path. 

Fig. 3.5.24. Possible helical configurations of disclination pairs in twisted nematics or cholesterics of large pitch (see figs. 4.2.2 and 4.2.3).

We now consider defect structures in the cholesteric liquid crystal. Treating the cholesteric as a spontaneously twisted nematic,... 

The Volterra process for creating these disclinations is the same as for nematic disclinations. For the screw disclination the plane of cut is parallel to the cholesteric twist axis while for the edge disclination it is perpendicular to it. 

Fig. 4.5.5. Theoretical variation of the apparent viscosity with pitch P = 2n/q for flow normal to the helical axis of a cholesteric (or twist nematic) at low shear rates. Plot of versus P for twisted PAA. The separation between the...

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. ... 

As with thermotropic nematics, the addition of optically active species to lyotropic nematic phases gives lyotropic cholesteric phases. Whilst details of their structures are not fully established they appear to follow the general pattern outlined above. The cholesteric twist would appear to derive from the packing of optically active mole-... 

Perhaps one of the most important applications of chiral induction is in the area of liquid crystals. Upon addition of a wide range of appropriate chiral compounds, the achiral nematic, smectic C, and discotic phases are converted into the chiral cholesteric (or twisted nematic), the ferroelectric smectic C and the chiral discotic phases. As a first example, we take the induction of chirality in the columns of aromatic chromophores present in some liquid-crystalline polymers. " The polymers, achiral polyesters incorporating triphenylene moieties, display discotic mesophases, which upon doping with chiral electron acceptors based on tetranitro-9-fluorene, form chiral discotic phases in which the chirality is determined by the dopant. These conclusions were reached on the basis of CD spectra in which strong Cotton effects were observed. Interestingly, the chiral dopants were unable to dramatically influence the chiral winding of triphenylene polymers that already incorporated ste-reogenic centers. 

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