Liquid cyanobiphenyl

The dimer model proposed by Wilson [83] was found not to exhibit a nematic phase but smectic A and B phases and so, although semi-realistic features are included, the model is not able to reproduce the behaviour of real dimers such as the a,co-bis(4 -cyanobiphenyl-4-yloxy) [87], which exhibit nematic phases, although liquid crystal dimers exhibiting smectic phases are also known [88]. In these simulations, the GB-GB interaction appears to be too strong and so the system forms a smectic phase in which the GB and LJ units... 

The first report on the liquid crystalline properties of these compounds was published by Gray and Mosley [44] in 1976. The series of 4 -n-alkyl-4-cyanobiphenyls (CBn) have been widely studied by different methods due to their readily accessible nematic ranges around room temperature. The compounds have the phase sequences crystal-nematic-isotropic for CBS, CBIO, and monotropic nematic for CBS, CB4 crystal-smectic A-nematic-isotropic for CB9 crystal-smectic A-isotropic for CBll. The lower homologous CB2 is nonmesogenic. The general chemical structure of the compounds CBn is presented in Fig. 1. 

Liquid-crystalline complexes (metallomesogens) containing platinum(II) are new types of materials that have been the subject of several studies. These have largely included complexes of the type trans-[PtX2L2] (X = C1, L = cyanobiphenyls 229 X = C1, carboxylate, L = 4-alkoxy-4 stilbazoles 230 X = C1, L = 2,4-, 3,4-, or 3,5-dialkoxystilbazoles, 2,3,4-, 2,4,5-, or 3,4,5-trialkoxystilbazoles).231,232 Their liquid-crystalline properties have also been reported. 

Each of these couplings is inversely proportional to the cube of the distance between the atoms concerned, and all the dipolar couplings depend on the degree of orientation of the molecules. The ratios of couplings thus depend on the ratios of distances in the molecule, and from them the entire molecular structure, except for the overall size, may be determined. Studies of silyl compounds dissolved in cyanobiphenyl liquid crystals have yielded the following HSiH angles ... 

Cyanation of aromatic hydrocarbons, also a carbon-carbon coupling reaction, is achieved in the case of anthracene in MeCN-Et4NCN to yield 54% 9,10-dicyanoanthracene [165]. The cyanation is simplified when it is carried out in an emulsion system (aqueous sodium cyanide, dichloromethane, and TBAHSO4). Its synthetic utility in this mode has been demonstrated for the preparation of 4-alkoxy-4-cyanobiphenyls, a class of liquid crystals [166]. 

The Tfj-symmetrical hexaaddition pattern also represents an attractive core tecton for dendrimer chemistry [26, 31, 63-67]. Examples for such dendrimers, involving a core branching multiplicity of 12, are 38 and 39 [63, 64], Addition of six mesotropic cyanobiphenyl malonate addends produced the spherical thermotropic liquid crystal 40 [65], DSC and POM investigations revealed a smectic A phase between 80 and 133 °C. Interestingly, this spherical and highly symmetrical compound gives rise to liquid crystallinity despite the absence of molecular anisotropy. 

Sensitized for blue-green or red light, photoconductive polyimides and liquid crystal mixtures of cyanobiphenyls and azoxybenzene have been used in spatial light modulators [255-261]. Modulation procedure was achieved by means of the electrically controlled birefringence, optical activity, cholesteric-nematic phase transition, dynamic scattering and light scattering in polymer-dispersed liquid crystals. 

In 2003, Sugimoto and Kanie published what appears to be the first claim on the formation of nematic-like one-dimensional ordering in liquid crystal-nanoparticle hybrid materials. Different shapes of Ti02 nanoparticles were hybridized with two structurally different rod-like liquid crystal amines (one based on a cyanobiphenyl and a second with a fluorinated cyclohexylbiphenyl core), but only the combination of spindle-like Ti02 nanorods (with an aspect ratio greater than 10) with the... 

Fig. 22 Nanoparticles decorated with pro-mesogenic dendronized or bent-core liquid crystal ligands nematic Fe304 mixed monolayer nanoparticles capped with dendronized cyanobiphenyl ligands and oleic acid (17) [132], and mixed monolayer, non-mesogenic gold nanoparticles decorated with bent-core liquid crystal and hexane thiolates (18) [547]...

Deschenaux et al. were likely first to use this combination of mesomorphic cyanobiphenyl-based dendrons, both mixed and homogeneous monolayer fashion, on gold nanoparticles with average sizes of 1.2 or 1.7 nm in diameter, but found no liquid crystal phase formation in the bulk aside from the pattern formation on TEM grids resembling a layer-like organization of the gold nanoparticles [546],... 

Gangadhara et al. have linked the cyanobiphenyl mesogen via a dicarbox-imide-group to an oxanorbornene ring system Vl-n, n=2-8 (see Fig. 4). Polymerization was carried out with Schrock type initiator 4. The dicarboximide linkage probably hindered the formation of LC phases even the introduction of relatively long spacers between the polymer backbone and the mesogen did not lead to liquid crystalline monomers or polymers [41]. 

The most simple molecular topology of such systems reported so far is a tetrahedral supermolecule obtained by reacting tetrakis(dimethylsiloxy)-silane with alkenyloxy-cyanobiphenyls (Fig. 22), as discussed previously. Such tetramers exhibit smectic A liquid crystal phases [179]. For such end-on materials, microsegregation at the molecular level favors the formation of the smectic A phases in preference to the nematic phase exhibited by the mesogenic monomers themselves. The use of different polyhedral silox-ane systems (Fig. 24) or the Ceo polyhedron as the template for multi- and polypedal hexakis(methano)fullerenes (Fig. 70) substituted with a large number of terminally attached mesogenic groups confirm the same tendency to the formation of smectic A phases (vide supra). 

Complementary dendritic hexamers based on a central scaffold made up of linked pentaerythritol and tri(hydroxymethyl)amino methane units have been found to also exhibit liquid-crystalline properties. This star-shaped scaffold was used to create supermolecules containing two different hemispheres, referred to thereafter as Janus supermolecular Hquid crystals (Fig. 76) [323,324]. One of the hemisphere contains three cyanobiphenyl end-groups, whereas the other lobe consists of three chiral phenyl benzoate mesogenic moieties laterally attached. The type of mesophase observed (N ... 

If the ratio f lf2 I is greater than unity the torques induced by the symmetric and antisymmetric strain rates respectively will never cancel out and the antisymmetric pressure will never vanish. This means that the director continues rotating for ever. The liquid crystal is said to be flow unstable and complicated flow patterns arise. TTiey have been studied comprehensively both experimentally and theoretically [30]. Some nematic liquid crystals are flow stable whereas others are not. For example, 4-n-pentyl-4 -cyanobiphenyl (5CB) is flow stable whereas 4-n-octyl-4 -cyanobiphenyl (8CB) is flow unstable. The only difference between this two substances is the length of the hydrocarbon chain attached to the cyanobiphenyl skeleton. Nematic liquid crystals that are flow stable usually become flow unstable close to the nematic-smectic A transition. The reason for this is that there is an emergent layer structure in the fluid that is incommensurate with the strain rate field. 

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