Smectic substituted mesogens

Unlike to the mesophase behaviour of laterally alkyl substituted mesogens, smectic phases can be stabilized depending on the substituents at the lateral phenyl ring. Figure 6 shows the polymorphism of a homologous series bearing a lateral 2-(4-n-alkan-... 

Table 11. Smectic C phases of laterally 2-(4-n-acyl-phenoxy )ethyloxycarbonyl substituted mesogens (the spac-er Z contains five units).

Properties have been determined for a series of block copolymers based on poly[3,3-bis(ethoxymethyl)oxetane] and poly [3,3-bis(methoxymethyl)oxetane]- (9-tetrahydrofuran. The block copolymers had properties suggestive of a thermoplastic elastomer (308). POX was a good main chain for a weU-developed smectic Hquid crystalline state when cyano- or fluorine-substituted biphenyls were used as mesogenic groups attached through a four-methylene spacer (309,310). Other side-chain Hquid crystalline polyoxetanes were observed with a spacer-separated azo moiety (311) and with laterally attached mesogenic groups (312). 

Spurred on by discussions on whether the smectic layers of the fluorocarbon-substituted polymers XXIII-m-n are induced by the immiscibility between hydrocarbon and fluorocarbon segments or by the fact that fluorocarbon segments form rod-like mesogenic units by themselves, Pugh et al. synthesized a series of siloxane-terminated monomers XXIV-m-n, with m=l,2 and n=4-S [79]. In these monomers, the rigid fluorocarbon segment was replaced by short polydimethylsiloxane (PDMS) segments that are also immiscible with hydrocarbons but are very flexible (Fig. 15). 

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). 

Polymers with methyl substitution on the central linkage in the stilbene mesogenic group have been prepared, Polymers 4 and 5, and show strictly nematic mesophases . The methyl group seems to act mostly to inhibit the existence of smectic order, but otherwise does not influence the mesophase formation or thermal stability very much. 

There have been many papers concerning liquid-crystalline polymers having azobenzenes in their side chains (Figure 14) because of the mesogenic nature of the azo chromophore. Liquid-crystalline polymers incorporating azobenzene moieties in their main chains (30) have also been prepared.102 A family of poly(acrylates) substituted with azobenzenes having chiral alkyl groups (31) showed smectic A as well as cholesteric phases.103 The photochromic behavior... 

We see in these examples that great effect can be created by substitutions on the two ends of the mesogenic cores. The consequence includes not only the formability of liquid crystal phases and transition temperatures, but also the types of the liquid crystalline phase. It is well known that substitution on the end with longer linear alkyls and alkoxyls favor the formation of smectic phases. One example for this remark has been given in Table 3.3. In the design of liquid crystal polymers, especially in the cases of side-group type and molecular shish-kebabs, the concept of end-substitution has been fully utilized. 

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