Nematogenic mesogens

It is clear that systems of hard ellipsoids exhibit an intriguingly simple phase behaviour with some resemblance to that of real nematogens. However, such systems cannot form smectic or columnar phases and in addition the phase transitions are not thermally driven as they are for real mesogens. As we shall see in the following sections the Gay-Berne potential with its anisotropic repulsive and attractive forces is able to overcome both of these limitations. 

ID and 2D 13C NMR were carried out in a series of novel nematogens by Bayle and co-workers to study the effects on the conformation and order due to the addition of lateral and/or terminal substituents.249 251 For example, lateral flexible substituents are found to adopt a mean conformation more or less parallel to the mesogenic core. As a result, lateral chains are less disordered than terminal chains. Nematogens containing polyoxyethylene ether (POE) chain as a lateral crown ether and terminal chain(s) have been... 

Copolymerization of two mesogenic monomers is, at the present time, the only pathway to obtain polymers with cholesteric mesophase (see Part 4.4). On the other hand, only by copolymerizing smectogenic and nematogenic monomers and investigating the properties of copolymers in a broad interval of compositions, is it possible to establish the principles of formation of each type of mesophase. We demonstrate... 

The first success was achieved when optically active (chiral) monomeric units were combined with a nematic LC polymer 105,123,143,144). The approach was based on the idea that a cholesteric mesophase may actually be realized as a helical nematic structure. Then by chemical binding of chiral and mesogenic units into a chain, accomplished by copolymerization or copolycondensation (in case of linear polymers) of nematogenic and optically active compounds, it was found feasible to twist a nematic mesophase and obtain copolymers of cholesteric type (Table 13). 

Fig. 32 A nematogenic supermolecular octasilsesquioxane, 35, with laterally appended mesogenic groups...

The chemical shifts allowed the local order parameters to be computed which indicated the uniaxial to biaxial nematic phase transition. The nematic phase of a deuterated fiuorenone nematogen has been studied by NMR and X-ray and evidence for biaxial order close to its glass transition temperature has been inferred. The possible symmetries of the biaxial nematic phase have been examined based on experimental results and it is concluded that a monoclinic symmetry rather than an orthorhombic symmetry that is more likely to be the cause for the observed phase biaxiality in thermotropic bent-core and calamitic-tetrapode nematic systems. Density functional theory has been employed in a detailed conformational study of a bent-core mesogen The chemical shielding... 

Figure 18 Synthesis of chiral LC copolymers by copolymerization of (1) nematogenic monomer with (2) chiral mesogenic monomer and with (3) chiral nonmesogenic monomers. Chirality of monomers is marked by an asterisk.

Tricatenars Several other mesogens of this type have been synthesized. They have a three-benzene-ring core and display the classical mesomorphic properties of rodlike mesogens. For instance, compounds 27 [5] and 28 [5,31] are smectogenic C and ne-matogenic, but when the alkyloxy chain is moved from meta to ortho position, the compound becomes only nematogenic. 

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