Terminal nematics

These structures were firstly observed for terminally polar mesogens [11, 12]. However, recent experiments give clear evidence of the presence of smectic A layering [37, 38], re-entrant nematic behaviour [39], two-dimensional lattices [40, 41] and smectic layering with incommensurate periodicities [42] for non-polar sterically asymmetric LCs. 

Fig. 6. Phase diagram for the binary mixture of terminally polar mesogens showii the reentrant nematic (N), monolayer (Ai), partially bilayer (Ad) and two-dimensional (C) phases (Lobko et al. [47])...

Derivatives of aliphatic alkynes (14 and 15) are more thermally unstable than 12, but they show SmA and N phases at low temperatures (below 130 °C). The type of phase and the mesophase stability depend on the length of both the terminal and the lateral chains. When both chains are elongated, the mesomorphism becomes metastable and compounds 14 display monotropic N and SmA transitions. Complexes IS, which contains an ester group with an opposite direction to that of complexes 14, display less stable nematic mesophases. 

Liquid crystals based on aliphatic isocyanides and aromatic alkynyls (compounds 16) show enantiotropic nematic phases between 110 and 160 °C. Important reductions in the transition temperatures, mainly in clearing points (<100 °C), areobtained when a branched octyl isocyanide is used. The nematic phase stability is also reduced and the complexes are thermally more stable than derivatives of aliphatic alkynes. Other structural variations such as the introduction of a lateral chlorine atom on one ring of the phenyl benzoate moiety or the use of a branched terminal alkyl chain produce a decrease of the transition temperatures enhancing the formation of enantiotropic nematic phases without decomposition. 

In cluster hydrides, the resonance for bridging hydrides tends to lie further upfield (— 15 to — 25 p.p.m.) than those for terminal M—H groups (0 to —15 p.p.m.), but exceptions exist.103 Nematic phase NMR has been used to determine M—H distances in cluster hydrides.110... 

In all cases of these rod-like molecules the fluorination of terminal chains leads to mesophase stabilization and to stabilization of smectic phases with respect to nematic phases. In most cases an increase of the melting temperatures11 and a stabilization... 

Upon addition of a terminal crown ether to the calamitic core unit, nematic phases were observed for 2, 3 in agreement with previous studies on substituted cyano biphenyls [25, 26]. 

Li and co-workers investigated derivatives of 43c,d [62]. Instead of the terminal heptyl chains, chiral (S)-2-methylbutyl or dodecyl chains were used. For the methylbutane side chain, a chiral smectic and a chiral nematic phase were observed and the clearing points were higher than in 43c,d due to the shorter chain while they were lower for the longer dodecyl side chains. It was also observed that the trans-compounds possess higher clearing temperatures compared to their c/.v-derivatives. 

Calamitic compounds which exhibit a smectic and/or nematic phase usually consist of a relatively rigid central core containing co-linear six-membered rings, either aromatic rings, such as 1,4-disubstituted-phenylene, 2,5-disubstituted-pyridine, 2,5-disubstituted-pyrimidine, 3,6-disubstituted-pyridazine, and alicyc-lic rings, such as /ra j-l,4-disubstituted-cyclohexane, 1,4-disubstituted-bicy-clo[2.2.2]octane, 2,5-disubstituted-dioxane. Heteroaromatic rings tend to lead to the formation of smectic phases rather than the nematic phase unless combined with a polar terminal function, such as a cyano group. The dependence of the liquid crystalline transition temperatures on the nature of... 

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