Mesogens ferroelectricity

In this section, we will present the crystal structures of chiral mesogenic compounds exhibiting ferroelectric liquid crystalline phases which are listed in Table 18 [152-166]. Moreover, four compounds of the list show antiferroelectric properties and two compounds form only orthogonal smectic phases. The general chemical structures of the investigated chiral compounds are shown in Fig. 27. 

Fig. 17a-c. Sketches of the molecular arrangements for the smectic structure with alternating layer-to-layer tilt a conventional and chevron smectic C layering in low molecular mass mesogens b ferroelectric hilayer chevron structures for achiral side-chain polymers c antiferroelectric hilayer chevron structures for achiral side-chain polymers. Arrows indicate the macroscopic polarization in the direction of the molecular tilt... 

When the mesogenic compounds are chiral (or when chiral molecules are added as dopants) chiral mesophases can be produced, characterized by helical ordering of the constituent molecules in the mesophase. The chiral nematic phase is also called cholesteric, taken from its first observation in a cholesteryl derivative more than one century ago. These chiral structures have reduced symmetry, which can lead to a variety of interesting physical properties such as thermocromism, ferroelectricity, and so on. 

Ferroelectric Macroscopic Racemate from Unichiral Mesogen... 

Figure 8.13 Hypothetical smectic mesogen with hinge in center of core is illustrated. Such material could in principal switch to ferroelectric state, which we term the SmAPp, upon application of electric field in plane of layers. If this state exists in well on configurational hypersurface, then ground-state structure is antiferroelectric, denoted SmAPA.

Figure 8.17 Structure and phase sequence of first banana-phase mesogen, reported by Vorlander in 1929, is given. Liquid crystal phase exhibited by this material (actually Vorlander s original sample) was shown by Pelzl et al.36a to have B6 stmeture, illustrated on right, in 2001. Achiral B6 phase does not switch in response to applied fields in way that can be said to be either ferroelectric or antiferroelectric.

From this discussion the clear similarity between the SmAPA and SmCsPA structures is easily seen. In addition, the suggestion of Brand et al.29 that a bilayer smectic with all anticlinic layer interfaces (the SmAPF) would produce an achiral ferroelectric smectic follows directly. The unanticipated tilt of the director in the tilt plane, leading to a chiral layer structure, seems to be a general response of the bent-core mesogens to the spontaneous nonpolar symmetry breaking occurring in these rigid dimer structures. 

Figure 8.29 Illustration showing how all-anticlinic bilayer smectic should be ferroelectric is given. In case of covalent dimers (bent-core mesogens), equilibrium tilt of director combined with anti clinic layer interfaces in bow plane provides SmCsPF ferroelectric banana structure.

This volume of Topics in Stereochemistry could not be complete without hearing about ferroelectric liquid crystals, where chirality is the essential element behind the wide interest in this mesogenic state. In Chapter 8, Walba, a pioneering contributor to this area, provides a historical overview of the earlier key developments in this field and leads us to the discovery of the unique banana phases. This discussion is followed by a view of the most recent results, which involve, among others, the directed design of chiral ferroelectric banana phases, which display spontaneous polar symmetry breaking in a smectic liquid crystal. 

Fig. 30 Selected examples of chiral rod-like mesogens with one fluorinated chain (77° C) one enantiomer is shown as example (SmCA = antiferroelectric SmC phase SmC = ferroelectric SmC phase SmCpi = ferrielectric SmC phase SmCa = helical SmC phase SmI = chiral tilted low temperature phase) [197-199]...

Chien and Cada [42] have prepared optically active and photoactive SCLC copolymers, 15, with the 4-alkoxyphenyl-4 -alkoxycinnamate chromophore, with the intention of creating LC polysiloxane networks that could be used to prepare macroscopically oriented organic ferroelectric polymers for electro-optical devices. Optical activity was introduced into the polymer by the use of a chiral spacer. Those copolymers which were mesogenic exhibited properties characteristic of a Sc. phase. UV-irradiation of thin films of the polymers in their mesomorphic states at 90°C, led to a loss of the IR absorption at 1635 cm-1 that is due to the cinnamate double bond, and to cross-linking. Long-term irradiation led to... 

Oge and Zentel [119] have studied a ferroelectric SCLC copolymer, 53, containing a photoisomerizable, chiral 4,4 -bisalkoxyazobenzene mesogen together with a chiral 4-alkoxyphenyl-4 -alkoxybenzoate mesogen that is photo-chemically unreactive at wavelengths where the azobenzene moiety can be photo-excited. This polymer has both a ferroelectric Sc. phase and a SA phase. Films... 

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