Hydrogen-bonded mixed crystals

Fig. 6.20 Phase diagram of dimer-forming hydrogen-bonded liquid crystal. The thin solid Une is the 1/N transition hne, the thick solid hne is the N/S, transition line, and the dotted line is the binodal. The hatched area is the metastable region. The dark gray area with U is the unstable region due to entropy difference between two different species of N structures. The light gray area with U is the unstable region due to mixing two different species of molecules. The open circle represents the critical solution point. Parameters are fixed at ha = "B = "a "b 0 = 30.0,...

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). 

Crystallization behavior in miscible blends containing crystallizable components has been extensively studied [174-180]. Generally, when a crystallizable component is mixed with an amorphous component its melting temperature goes down and its crystallinity lowers. The same trend has been reported for blends with intercomponent hydrogen bonding such as PCL/STVPh [181], PCL/poly(hydroxyl ether of bisphenol A) [182] and phenoxy resin/PEO [183]. 

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