Banana phases

Chiral Liquid Crystals from Achiral Molecules Banana Phases... 

This situation changed dramatically in 1996 with the discovery of strong electro-optic (EO) activity in smectics composed of bent-core, bowshaped, or banana-shaped achiral molecules.4 Since then, the banana-phases exhibited by such compounds have been shown to possess a rich supermolecular stereochemistry, with examples of both macroscopic racemates and conglomerates represented. Indeed, the chiral banana phases formed from achiral or racemic compounds represent the first known bulk fluid conglomerates, identified 150 years after the discovery of their organic crystalline counterparts by Pasteur. A brief introduction to LCs as supermolecular self-assemblies, and in particular SmC ferroelectric and SmCA antiferroelectric LCs, followed by a snapshot of the rapidly evolving banana-phase stereochemistry story, is presented here. 

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.

Figure 8.18 Smectic dimer of Watanabe, possessing an odd number of methylene units in linking group. This material self-assembles into intercalated smectic structure very similar to B6 banana phase. As for B6 phase, this achiral phase is also neither ferroelectric nor antiferroelectric.

While such behavior can be seen in achiral LC phases, driven by surface constraints as illustrated in Figure 8.11, further characterization of the phase responsible for the minority domains in the B2 banana phases shows this to be the first unequivocal example of a bulk fluid conglomerate. It is worth noting here that the EO behavior of the majority domains is achiral Stripes parallel to the layers switch to a SmA-like focal conic texture, which is identical for both signs of the field, as can be seen in Figure 8.22. This EO behavior very clearly appears achiral when observing the switching in motion. 

Figure 8.23 Illustration of chiral layer structure proposed for NOBOW high-temperature smectic banana phase is given. On left layer with (+) configuration is shown, while on right enantiomeric (—) configuration is illustrated. These mirror image fluid smectic layer configurations are not superposable.

A simple consideration of the synclinic banana phases in the context of the prior discovery of the Soto Bustamante-Blinov achiral antiferroelectric bilayer is illuminating. In Figure 8.28, the achiral antiferroelectric SmAPA bilayer structure is illustrated on the left. The layers are horizontal and normal to the plane of the page, and the tilt plane is vertical and normal to the plane... 

The discussion so far has described the observation of three of the four banana-phase diastereomers shown in Figure 8.26 two antiferroelectric isomers from NOBOW, and the ferroelectric banana phase of MHOBOW. Interestingly, discovery of the fourth isomer, the ferroelectric macroscopic... 

The author was supported by the Ferroelectric Liquid Crystal Materials Research Center (National Science Foundation MRSEC award No. DMR-9809555) during the writing of this chapter. The author thanks Professors Tom Lubensky, Leo Radzihovsky, and Joseph Gal for helpful discussions around the issue of terminology for reflection symmetry breaking, and especially Professor Noel Clark for his help on this and many other banana-phase issues. The author also thanks Dr. Renfan Shao for the photomicrographs shown in Figures 8.32 and 8.33. 

This banana phase nomenclature was established at the first international conference specifically focused on banana phases Chirality by Achiral Molecules, held in Berlin, Germany, in December, 1997. 

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