Host chiral smectics

The role of supramolecular chemistry in materials is perhaps expressed most impressively in liquid crystals, in which slight variations of chiral content can lead to dramatic influences in the properties of the mesophases. The helical sense of these mesophases is determined not only by intrinsically chiral mesogens but also by the use of dopants which more often than not interact with achiral host LCs to generate chiral phases (Fig. 7). These phenomena are important both scientifically and technologically, most notably for the chiral smectic and cholesteric liquid crystal phases [68-71]. These materials—as small molecules and as polymers [72,73]—are useful because their order... 

The phase transitions starting from the smectic phase were also observed in several doped systems [57-60]. The smectic LC host 8CB, doped with chiral molecules and azobenzene compounds, showed the phase transition from smectic to cholesteric due to the photo-induced isomerization of azobenzene molecules, and the prolonged irradiation drove the phase transition further to the isotropic phase. Matsui et al. also reported a chiral smectic C (SmC )-cholesteric (N ) phase sequence in azo-dye-doped ferroelectric LCs [57]. 

Finally, the difference of chirality enhancement in the N and SmC phases should be mentioned. As shown in Sect. 2.1, enhancement rate in SmC is about one order of magnitude larger than that in N. In the SmC chirality enhancement is attributed to two effects (1) the interaction between bent-core and chiral host molecules and (2) the coupling between ee, tilt, and spontaneous polarization. The latter effect is absent in the N phase and is an additional effect in SmC. Moreover, the chiral discrimination parameter AU is expected to be larger in SmC than in N because of a confined geometry, i.e., smectic layer. 

In chiral-racemic mixtures, the magnitude of Pg varies essentially linearly with the enantiomeric excess. Important for applications is the more general case of a mixture of a nonchiral smectic-C host with a chiral dopant. The relation between Pg and the concentration of the chiral dopant in such mix-... 

The synthesis of the first achiral host material that exhibits a smectic Cau phase [36] (achiral version of the antiferroelectric phase) is shown in Fig. 42. It can be seen that this material has three aromatic rings and two ester groups, but in addition it has a swallow-tail unit. This unit (for no apparent reason at the moment) stabilizes the formation of smectic Cai, phases. The material like a ferroelectric host can be doped with a chiral dopant to give an antiferroelectric mixture. 

---