Polar Achiral Systems

In fact, two new representatives of polar achiral systems have been discovered quite recently antiferroelectric polymer-monomer mixtures [286] and ferroelectric biaxial smectic A phases composed of ba-nana-like molecules [287]. 

We note that the bilayer smectic phase which may be formed in main-chain polymers with two odd numbered spacers of different length (Fig. 7), should also be polar even in an achiral system [68]. This bilayer structure belongs to the same polar symmetry group mm2 as the chevron structure depicted in Fig. 17b, and macroscopic polarization might exist in the tilt direction of molecules in the layer. From this point of view, the formation of two-dimensional structure of the type shown in Fig. 7, where the polarization directions in neighbouring areas have opposite signs, is a unique example of a two dimensional antiferroelectric structure. 

Bearing in mind the odd-even effect, I tried to synthesize new polymer types in order to express the ferroelectric phase in an achiral system. The opportunity to study chiral ferroelectric liquid crystals was ripe at that time, as I already mentioned in the opening sentence. Their discoverer Mayer [118] argued that by introducing a chiral molecule into a Sc phase, the twofold axis of the Sc phase becomes the polar axis because of the extinction of a vertical mirror symmetry (Fig. 9.20). The reduction of the symmetry by the introduction of chirality into the system is in a sense conventional, simple, and straightforward. 

Liquid crystal molecules usually tilt in the same direction over the smectic layers (synclinic [212]) in the smectic C (SmC) phase. However, in one of the smectic A (SmA) phases, called de-Vries phase [213,214], molecules tilt but the tile direction is random so that the overall molecular tilt cannot be recognized optically. Frustration can be produced between aligning and random orders [215]. There is another style of tilt, in which the tilting direction is aligning in one direction in each smectic layer however, tilting direction alternates between the adjacent layers (anticlinic [212]). It has been well known that the introduction of chirality into the synclinic and anticlinic stmctures produces the ferroelectric and antiferroelectric properties, respectively. Frustration between the ferroelectric and antiferroelectric properties produces the ferroelectric structure in which the spontaneous polarization is partially canceled by the different magnitude between plus and minus polarization directions [216, 217]. The anticlinic order, NOT the antiferroelectric order, has been reported to be created by achiral systems [218, 219], indicating that the frustration between synclinic and anticlinic structures occurs, without any polar effects. The clinicity is determined by the style of the molecular order between the adjacent smectic layers, and therefore, the molecular structures at the peripheral... 

Ekgorg-Ott et al. (1997). An interesting trend was discovered when considering the relative amount of D-theanine present in the samples. The teas of the highest grades consistently contained the lowest amounts of D-theanine. The theanine achiral-chiral system configuration included a C18 column operated in the reverse-phase mode and a y-cyclodextrin CSP in the polar organic mode. 

In 1994 we published the first chiral dendrimers built from chiral cores and achiral branches [ 1,89], see for instance dendrimer 57 with a core from hydroxy-butanoic acid and diphenyl-acetaldehyde and with twelve nitro-groups at the periphery (Fig. 21). As had already been observed with starburst dendrimers, compound 57 formed stable clathrates with many polar solvent molecules, and it could actually only be isolated and characterized as a complex [2 (57- EtO-Ac (8 H20))]. Because no enantioselective guest-host complex formation could be found, and since compounds of type 57 were poorly soluble, and could thus not be easily handled, we have moved on and developed other systems to investigate how the chirality of the core might be influencing the structure of achiral dendritic elongation units. 

The starting system is achiral (plates at 90° with isotropic fluid between), but leads to the formation of a chiral TN structure when the fluid becomes nematic. In this case, enantiomeric domains must be formed with equal likelihood and this is precisely what happens. The size of these domains is determined by the geometry and physics of the system, but they are macroscopic. Though the output polarization is identical for a pair of heterochiral domains, domain walls between them can be easily observed by polarized light microscopy. This system represents a type of spontaneous reflection symmetry breaking, leading to formation of a conglomerate of chiral domains. 

Figure 8.12 Longitudinal sheets with antiparallel polar symmetry are illustrated for achiral SmCA and SmC phases. Since it is not possible to switch to ferroelectric state in such system upon application of electric field, these structure should not be considered antiferroelectric.

Figure 8.16 Illustration of symmetry of Soto Bustamante-Blinov achiral antiferroelectric smectic LC with finite number of layers. Such systems can be studied using DRLM technique with thin freely suspended smectic films, (a) With even number of bilayers, film has local C2 symmetry, and therefore no net electric polarization, (b) With odd number of bilayers, film has local Cnv symmetry and is therefore polar, with net spontaneous electric polarization in plane of layers.

Even starting from achiral molecules it is in some systems possible to achieve crystallization in a chiral structure. Perhaps one of the most striking achievements in organic solid-state chemistry has been the trapping of the chirality of such a crystal as the chirality of the stable product of chemical reactions in the crystal. Such asymmetric synthesis has been reviewed (255), and a recent book (256) also provides a thorough discussion of chirality in crystals. The related and fascinating topic of the chemical consequences of the presence of a polar axis in some organic crystals has also been reviewed (257). 

The absorption of two different photons also significantly increases the number of polarization variables arising in the rate equations. The ability of the experimentalist to independently vary the polarization and experimental configuration of the two laser beams allows a choice of values for these polarization parameters which significantly increases the amount of information that can be derived from the spectra. In contrast to the case of single-beam excitation, this also affords the opportunity to observe the induction of circular dichroism in a system of achiral molecules. 

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