Phase behavior, chiral crystals

Liquid crystalline behavior occurs in the exocuticle of certain classes of beetles. The bright iridescent colors that are reflected from the surface of Scarabaeid beetles originates from a petrified chiral nematic stmctural arrangement of chitin crystaUites in the exocuticle (38). It is suggested that this chiral nematic texture forms spontaneously in a mobile, Hquid crystal phase that is present during the initial stages of the exocuticle growth cycle. 

To produce novel LC phase behavior and properties, a variety of polymer/LC composites have been developed. These include systems which employ liquid crystal polymers (5), phase separation of LC droplets in polymer dispersed liquid crystals (PDLCs) (4), incorporating both nematic (5,6) and ferroelectric liquid crystals (6-10). Polymer/LC gels have also been studied which are formed by the polymerization of small amounts of monomer solutes in a liquid crystalline solvent (11). The polymer/LC gel systems are of particular interest, rendering bistable chiral nematic devices (12) and polymer stabilized ferroelectric liquid crystals (PSFLCs) (1,13), which combine fast electro-optic response (14) with the increased mechanical stabilization imparted by the polymer (75). 

Abstract It is well known that spontaneous deracemization or spontaneous chiral resolution occasionally occurs when racemic molecules are crystallized. However, it is not easy to believe such phenomenon will occur when forming liquid crystal phases. Spontaneous chiral domain formation is introduced, when molecules form particular liquid crystal phases. Such molecules possess no chiral carbon but may have axial chirality. However, the potential barrier between two chiral states is low enough to allow mutual transformation even at room temperature. Therefore the systems are essentially not racemic but nonchiral or achiral. First, enhanced chirality by doping chiral nematic liquid crystals with nonchiral molecules is described. Emphasis is made on ester molecules for their anomalous behavior. Second, spontaneous chiral resolution is discussed. Three examples with rod-, bent-, and diskshaped molecules are shown to give such phenomena. Particular attention will be paid to controlling enantiomeric excess (ee). Actually, almost 100% ee was obtained by applying some external chiral stimuli. This is very noteworthy in the sense that we can create chiral molecules (chiral field) without using any chiral species. 

Tosoni M, Laschat S, Baro A. Synthesis of novel chiral hquids and their phase behavior in mixtures with smectic and nematic liquid crystals. Helv. Chim. Acta. 2004. 87, 2472-2479. 

After the discovery of the liquid crystal behavior of HPC in solution, a multitude of studies have reported the ordering phenomena of different cellulose derivatives, according to the examples given below [90]. Figure 14.6 presents the optical microscopy of an aqueous suspension of microcrystalline cellulose at a concentration of 16 wt%, where the nematic field and a chiral nematic phase typical to a fingerprint texture maybe observed 10 minutes and respectively 1 day after the preparation of the suspension [116]. 

Due to the important role of chirality in liquid crystals, a large number and variety of chiral chemical compounds have been developed. This chapter describes the most important molecular fragments and classes of chemical structures (Section 4.2) which provide both chirality and mesogenic properties. The form of chiral phases depends on the principles of the mesophase formation (Section 4.3). Some relations between the molecular chirality and the appearance of mesophase chirality are discussed and chiral dopants are classified (Section 4.4). With respect to the mesophase behavior and to optical and electro-optical applications, it is important to know how the mesogenic chirality can be modified, e.g., chemically by photoisomerization, or by changes of temperature or composition for certain suitable compounds (Section 4.5). Finally, chiral liquid crystals provide not only optical and electro-optical applications but also applications in Chemistry, e.g., as chiral solvents for synthesis, chiral stationary phases in chromatography, or chemical sensors (Section 4.6). 

The orthogonal arrangement of the disc-like molecules in the columns of and D id phases makes these phases uniaxial, while the tilted phases (Drd and Doh.d and Dt) are optically biaxial. There are two additional columnar phases labeled as and that have not yet been classified. The columnar phases were discovered before the observation of a nematic phase for disc-like molecules. Both chiral nematic phases and the re-entrant behavior have now been observed in discotics. The phase diagram and molecular structure of a typical discotic liquid crystal are shown in Fig. 1.11. Finally, it is noted that another classification scheme for the discotic mesophases has been used [1.26], which is based on the notation used for the conventional smectics. 

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