Dopants chiral nematics

If the molecules are chiral or if a chiral dopant is added to a discotic Hquid crystal, a chiral nematic discotic phase can form. The director configuration ia this phase is just like the director configuration ia the chiral nematic phase formed by elongated molecules (12). Recendy, discotic blue phases have been observed. 

The polyamides are soluble in high strength sulfuric acid or in mixtures of hexamethylphosphoramide, /V, /V- dim ethyl acetam i de and LiCl. In the latter, compHcated relationships exist between solvent composition and the temperature at which the Hquid crystal phase forms. The polyamide solutions show an abmpt decrease in viscosity which is characteristic of mesophase formation when a critical volume fraction of polymer ( ) is exceeded. The viscosity may decrease, however, in the Hquid crystal phase if the molecular ordering allows the rod-shaped entities to gHde past one another more easily despite the higher concentration. The Hquid crystal phase is optically anisotropic and the texture is nematic. The nematic texture can be transformed to a chiral nematic texture by adding chiral species as a dopant or incorporating a chiral unit in the main chain as a copolymer (30). 

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. 

Mixtures of a nematic liquid crystal (LC or LC ) with small quantities of gold nanoparticles coated with alkylthiolates (<5 wt%) including an alkylthiolate functionalized with a chiral group have been studied (Figure 8.29) [72]. All mixtures show nematic mesophases with transition temperatures and phase stability very similar to those oftheliquid crystal precursors LC or LC. The introduction ofachiral center into the mixtures (mixtures of Au ) produce chiral nematic mesophases. A similar result is obtained in mixtures of Au and LC doped with the chiral dopant (s)-Naproxen. 

The study of the cholesteric mesophases obtained by doping thermotropic nematics with chiral, nonracemic compounds, has lead to relevant information about the stereochemistry of the dopants. Chiral interactions change the structure of the phase and therefore molecular chirality can be mapped onto an achiral (nematic) phase to yield a superstructural phase chirality. In 1984 Sol-ladie and Zimmermann published the first review summarizing the state of the art at that time.52 Later on, several review articles updated this subject.53-55... 

The cholesteric phase in hquid crystals is analogous to the nematic phase but it is formed by materials that contain a chiral centre, initially derivatives of cholesterol (5.3), hence the name cholesteric LCs. Since synthetic chiral molecules can also be used on their own or as dopants for nematic LCs, e.g. (5.4), chiral nematic is probably a more appropriate term for these materials. 

The classical cholesteric phase materials show only a weak anisotropic interaction with electric fields and hence are of limited use in electro-optical response applications. Cholesteric phases for these outlets are consequently produced by adding chiral dopants to nematic liquid crystals. 

One alternative approach is to use photoisomerisable chiral compounds where the E and Z isomers have different helical twisting powers, e.g. menthone derivatives. By incorporating co-polymers, prepared from menthone containing monomers and cyano esters (5.5), as dopants into nematic LC mixtures materials, e.g. a mixture of cyanobiphenyls and cyanoterphenyls (E7 available from Merck), colour change can be effected by irradiating with UV light (365 nm). The colour obtained is dependent... 

The polyamides are soluble in high sirength sulfuric acid or in mixtures of hexamelhylphosphoiamide. AMV-diinethylaeciamidc. and l.ifT. The liquid-crystal phase is optically anisotropic and the texture is nematic. The nematic texture can he transformed lo a chiral nematic texture by adding chiral species us a dopant or incorporating a chiral unit in the main chain as a copolymer. 

Several exciting phenomena described for non-chiral nematic systems were also reported for nanoparticle-doped chiral nematic liquid crystals. We mentioned the work of Kobayashi et al., who, most notably, demonstrated a frequency modulation twisted nematic (FM-TN) mode and fast switching characteristics using metal nanoparticles as dopants [301-307, 313, 314],... 

Fig. 10 (a, b) Schematic mechanism demonstrated for a reflective color M-paper with magnetically controllable characteristics, (c, d) The intensity of magnetic field dependence on the reflection spectra of chiral nematic mixtures doped with magnetite nanoparticles that are surface modified with oleic acid and a chiral pyridine-based dopant, as well as photographs of both formulations before and after a magnetic field of 1,000 GS was applied (see photograph insets above) [364], (Copyright 2010, Taylor Francis)... 

The electro-optical characteristics of multiplexed STN-LCDs exhibit a significant dependence on temperature. This has to be compensated in order to avoid variations of the optical performance of the display with temperatures. This can be achieved electronically. However, this problem can also be solved by the use of optically active, chiral dopants. The capacitive threshold voltage of a chiral nematic mixture depends on the pitch of the mixture ... 

The electrode surfaces of a normal LCD sandwich cell d 8-10 pm) are coated with an alignment layer in order to induce a planar alignment of a host (chiral) nematic mixture containing the dichroic dye of positive dichroism and a chiral dopant. Due to the absence of polarisers a very thin mirror can be incorporated within the cell on top of the rear glass plate electrode in direct contact with the guest-host mixture, see Figure 3.15. 

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 ... 

Bobrovsky AY, Shibaev VP. 2002. Chiral nematic polymer mixture containing crosslinker and photosensitive chiral dopant new type of materials with tunable photooptical properties. Adv Funct Mater 12(5) 367 372. 

Ruslim C, Ichimura K. 2002. Photoswitching in chiral nematic liquid crystals inter action selective helical twist inversion by a single chiral dopant. J Mater Chem... 

Van de Witte P, Galan JC, Lub J. 1998. Modification of the pitch of chiral nematic liquid crystals by means of photoisomerization of chiral dopants. Liq Cryst 24(6) 819 827. 

It was recently shown that copper complexes derived from (5)-2-(2-hydroxyar oxazoline ligands ((242) x= 1 R = CH3, CHMe2, CH2CHMe2 x= 1, 2 R = C HCH3CH2CH3) exhibited a very broad SmA phase, from 60°C to around 150 190°C. Used as chiral dopants (ca. lOmol.%), a chiral nematic phase was induced systematically in all the systems, even those with x = 0, with, in some cases, an additional SmA phase being observed. 

R. Thomas, Y. Yoshida, T. Akasaka, N. Tamaoki, Influence of a change in helical twisting power of photoresponsive chiral dopants on rotational manipulation of micro-objects on the surface of chiral nematic liquid crystalline films. Chem. Eur. J. 18, 12337-12348 (2012)... 

T. Yamaguchi, T. Inagawa, H. Nakazumi, S. Irie, M. Irie, Photoswitching of helical twisting power of a chiral diarylethene dopant pitch change in a chiral nematic liquid crystal. Chem. Mater. 12, 869-871 (2000)... 

Chiral Dopants and Chiral Nematic Liquid Crystals Acetylene Polymerization in Chiral Nematic Liquid Crystal Characterization of Helical Polyacetylene Film... 

Chiral Dopants and Chiral Nematic Liquid Crystals... 

FIGURE 3.1 (See color insert following page 14-20.) Chiral nematic LC induced by the addition of chiral dopant into... 

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