Unusual Core Systems

This brief account of methods for the synthesis of nematic liquid crystals concentrates on the most frequently encountered core systems, linking and terminal groups the synthetic methods presented are often applicable to more unusual nematogens and to compounds showing other mesophases (see V. Vill in Volume 1, Chapter IV on General Synthetic Strategies). 

In addition to tire standard model systems described above, more exotic particles have been prepared witli certain unusual properties, of which we will mention a few. For instance, using seeded growtli teclmiques, particles have been developed witli a silica shell which surrounds a core of a different composition, such as particles witli magnetic [12], fluorescent [13] or gold cores [14]. Anotlier example is tliat of spheres of polytetrafluoroetliylene (PTFE), which are optically anisotropic because tire core is crystalline [15]. 

Using similar methodology, macrocycle 126 was prepared, as well as the unusual monoene 127 [76]. Considerable debate in the literature over the last thirty years has focused on whether dehydrobenzoannulenes are able to sustain induced ring currents [5al. Although fusion of arenes to the annulenic core provides rigidity and stability, this also weakens the diatropicity/paratropicity of the macrocycle significantly. Until quite recently, the number of planar systems available for study was limited however, with the the addition of 123 and 126, the series of alkyne-linked, tribenzo-fused dehydroannulenes is complete from... 

The unusual carbocation structure 53, a linear 5-center 4-electron C-H-C-H-C array can be derived from three anthracenes joined up around a C-H-C-H-C core.73 The GIAO-DFT computed H and 13C NMR chemical shifts for the bridging hydrogens (2.9 ppm) and carbons (112 and 182 ppm) of the 5-center array differ considerably from those found in typical 3-center 2-electron systems. 

Figure 1 shows a reversed micelle where the bulk solvent is a hydrocarbon and the core is a water pool surrounded by surfactant. These systems possess unique features as the physical properties of the water pools only start to approach those of bulk water at high water content when the pool radii are >150 pools with radii as small as 15 can be constructed (1, 25). These systems have been used to investigate the nature of several inorganic reactions by stopped flow methods (26, 27). They have also been used to produce so-called naked ions, i.e., ions that possess a minimum of aqueous solvation (28). The system strongly promotes many reactions, a fact attributed to the unusual nature of the water in this system. 

Thermodynamic modelling of solution phases lies at the core of the CALPHAD method. Only rarely do calculations involve purely stoichiometric compounds. The calculation of a complex system which may have literally 100 different stoichiometric substances usually has a phase such as the gas which is a mixture of many components, and in a complex metallic system with 10 or 11 alloying elements it is not unusual for all of the phases to involve solubility of the various elements. Solution phases will be defined here as any phase in which there is solubility of more than one component and within this chapter are broken down to four types (1) random substitutional, (2) sublattice, (3) ionic and (4) aqueous. Others types of solution phase, such as exist in polymers or complex organic systems, can also be modelled, but these four represent the major types which are currently available in CALPHAD software programmes. 

Bent-core liquid crystals are especially interesting materials for basic research as in these systems the polar and tilt order are decoupled and polarization splay seems to be an inherent property of the system. Both effects lead to a variety of structures with unusual properties, e.g., formation of the 2D density modulated phases built of the smectic layers fragments. We have presented the current knowledge... 

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