Section Chiral Crystallization

We can conclude this section noting that understanding chiral crystallization of helical polymers is still hardly satisfactory, but quite certainly different mechanisms are likely to apply for different polymers and different crystallization conditions. A lot of experimental work still needs to be carried out if we want to progress beyond speculation and generalization of results that may in fact apply only to very specific instances. 

We illustrated in Section II why conventional X-ray diffraction cannot distinguish between enantiomorphous crystal structures. It has not been generally appreciated that, in contrast to the situation for chiral crystals, the orientations of the constituent molecules in centrosymmetric crystals may be unambiguously assigned with respect to the crystal axes. Thus, in principle, absolute configuration can be assigned to chiral molecules in centrosymmetric crystals. The problem, however, is how to use this information which is lost once the crystal is dissolved. 

In terms of die original discussion of Section II, what one needs to know is the orientation of die chiral molecule in a chiral crystal relative to die crystal axes. The absolute orientation of the molecule or of a sequence of molecules in the crystal can be determined by high-resolution electron microscopy, especially in cases like rubidium tartrate or other organometallics in which die problem is to determine the relative position of die heavy metal km with respect to die... 

The effect of the cyano substituent seems to dominate in 43 the bond opposite to it is the shortest91. The C—C (N) bond has the same length, 1.447 (4) A, as in other cyanocyclo-propanes (Section III.D). The phenyl group adopts the bisected conformation. Crystallization leads to a spontaneous resolution, which is rather rare among phenylcy-clopropanes, and a conglomerate of chiral crystals is formed91. 

In this section, diastereomeric crystallization is presented as a driving force -or internal selection pressure - to resolve dynamic diastereomeric systems. The dynamic diastereomeric systems are generated from reversible covalent bond formation, leading to compounds carrying chiral carbon centers under thermodynamic control. The dynamic systems can represent more variety of the possible diastereomer adducts. The selective diastereomers, A —B, , are subsequently chosen from the dynamic system by self-transformation and/or self-preferential crystallization. When the selective product C , is formed, the ratio of its corresponding diastereomer adducts A -Bm in the dynamic system will be decreased. The equilibrium in the dynamic system will force the reproduction of the intermediate until the resolution has reached completion. In the end, only one diastereomeric product Cnm is selectively crystallized and easily purified from the solution. 

The chiral 1-ce group was produced from the achiral 2-ce group in the photoisomerization as shown in Scheme 5.1. This gave an idea that the asynunetric induction would be observed if the isomerization occurs in the chiral crystal environment. A very high optical yield ( 82 % ee) was observed using / -2-amino-2-phenylethanol as an axial base ligand [14]. This section describes the chirality generation in the two types of 2-ce complex crystals with perpendicular and parallel conformations. 

As witli tlie nematic phase, a chiral version of tlie smectic C phase has been observed and is denoted SniC. In tliis phase, tlie director rotates around tlie cone generated by tlie tilt angle [9,32]. This phase is helielectric, i.e. tlie spontaneous polarization induced by dipolar ordering (transverse to tlie molecular long axis) rotates around a helix. However, if tlie helix is unwound by external forces such as surface interactions, or electric fields or by compensating tlie pitch in a mixture, so tliat it becomes infinite, tlie phase becomes ferroelectric. This is tlie basis of ferroelectric liquid crystal displays (section C2.2.4.4). If tliere is an alternation in polarization direction between layers tlie phase can be ferrielectric or antiferroelectric. A smectic A phase foniied by chiral molecules is sometimes denoted SiiiA, altliough, due to the untilted symmetry of tlie phase, it is not itself chiral. This notation is strictly incorrect because tlie asterisk should be used to indicate the chirality of tlie phase and not tliat of tlie constituent molecules. 

In this section, we will neglect the crystal structures of the mesogenic perfluorinated phenyl benzoates [23-27], benzoic acids [6, 28-31], cinnamic acids [7, 32, 33], dicarboxylic acids [34, 35], and cinnamate compounds [8, 36-40]. The single crystal X-ray analyses of chiral mesogenic carboxylates are described in Sect. 6. 

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. 

Sulfoxides without amino or carboxyl groups have also been resolved. Compound 3 was separated into enantiomers via salt formation between the phosphonic acid group and quinine . Separation of these diastereomeric salts was achieved by fractional crystallization from acetone. Upon passage through an acidic ion exchange column, each salt was converted to the free acid 3. Finally, the tetra-ammonium salt of each enantiomer of 3 was methylated with methyl iodide to give sulfoxide 4. The levorotatory enantiomer was shown to be completely optically pure by the use of chiral shift reagents and by comparison with a sample prepared by stereospecific synthesis (see Section II.B.l). The dextrorotatory enantiomer was found to be 70% optically pure. 

The earliest approach to explain tubule formation was developed by de Gen-nes.168 He pointed out that, in a bilayer membrane of chiral molecules in the Lp/ phase, symmetry allows the material to have a net electric dipole moment in the bilayer plane, like a chiral smectic-C liquid crystal.169 In other words, the material is ferroelectric, with a spontaneous electrostatic polarization P per unit area in the bilayer plane, perpendicular to the axis of molecular tilt. (Note that this argument depends on the chirality of the molecules, but it does not depend on the chiral elastic properties of the membrane. For that reason, we discuss it in this section, rather than with the chiral elastic models in the following sections.)... 

The second issue concerns the anisotropy of the membrane. The models presented in this section all assume that the membrane has the symmetry of a chiral smectic-C liquid crystal, so that the only anisotropy in the membrane plane comes from the direction of the molecular tilt. With this assumption, the membrane has a twofold rotational symmetry about an axis in the membrane plane, perpendicular to the tilt direction. It is possible that a membrane... 

An asymmetric photosynthesis may be performed inside a crystal of -cinnamide grown in the presence of E-cinnamic acid and considered in terms of the analysis presented before on the reduction of crystal symmetry (Section IV-J). We envisage the reaction as follows The amide molecules are interlinked by NH O hydrogen bonds along the b axis to form a ribbon motif. Ribbons that are related to one another across a center of inversion are enantiomeric and are labeled / and d (or / and d ) (Figure 39). Molecules of -cinnamic acid will be occluded into the d ribbon preferentially from the +b side of the crystal and into the / ribbon from the — b side. It is well documented that E-cinnamide photodimerizes in the solid state to yield the centrosymmetric dimer tnixillamide. Such a reaction takes place between close-packed amide molecules of two enantiomeric ribbons, d and lord and / (95). It has also been established that solid solutions yield the mixed dimers (Ila) and (lib) (Figure 39) (96). Therefore, we expect preferential formation of the chiral dimer 11a at the + b end of the crystal and of the enantiomeric dimer lib at the —b end of the crystal. Preliminary experimental results are in accordance with this model (97). 

This approach may also be applied to racemic bilayers built up from homo-chiral Langmuir-Blodgett monolayers. By measuring the two-dimensional diffraction pattern from such a bilayer it is possible to deduce the molecular chirality of each of the two monolayers in the order they were inserted to construct the bilayer. This approach can be extended to multilayers. Thus, in principle, we close the circle started in Section IV-G-1. It is possible to assign the absolute configuration of chiral molecules in centrosymmetric crystals provided that one can construct the crystal (in this case the multilayer) by adding homochiral layers one by one. 

All the crystal forces that we treat in this section can be considered in terms of the recognition between a given, reference molecule and the cavity it is to occupy in the crystal. In chiral systems the cavity is clearly of different shape in the d and / crystals, and this generally results in differential incorporation of R and S molecules. However, in molecules containing the sec-butyl group, discrimination is often ineffective. This is because the two enantiomers can assume different conformations with very similar external shapes, and they can then interchangeably enter the same cavity in the crystal. This effect was recognized some time ago (55), and recently its consequences have been studied in detail (56). In the case where two enantiomers may readily replace one another in the crystal, it follows that there is a tendency to conformational disorder (see biphenyl, above), and in many cases, the resolved enantiomers and the racemates are isostructural. 

Another mechanism of chiral amplification that extends over an even larger scale has been reported by Huck et al. [119] The molecule 12-(9 H-thioxantbene-9 -yli-dene-12H-benzo[a]xanthene (Fig. 11.6), which has no chiral center, nevertheless exists, like the helicenes, in two chiral forms defined by their enantiomeric configurations. Consistent with the discussion in Section 11.2.3, a small net handedness (ca. 0.7 %) could be induced in racemic solutions of this molecule by use of ultraviolet CPL. However, introducing 20 wt% of this molecule, which contained a 1.5% chiral excess of one roto-enantiomer, into a nematic phase of liquid crystals produced macroscopic (100 pm) regions of a chiral cholesteric liquid crystal phase. The... 

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