Enantiotropic smectic mesophase

The thermotropic behavior of both the isotactic and syndiotactic poly n-[4 -(4"-methoxyphenyl)phenoxy]alkyl methacrylate s is summarized in Table 11. All of the tactic polymers crystallize. With the exception of poly 2-[4 -(4"-methoxyphe-nyl)phenoxy]ethyl methacrylate] (n=2), the melting temperature of the isotactic polymers is almost independent of the spacer length. In contrast, the syndiotactic polymers melt with a large odd-even alternation. However, only the syndiotactic polymers with at least four carbons in the spacer exhibit an enantiotropic smectic mesophase, which occurs over only a very narrow temperature range. The greater order of the isotactic polymers is evidently due to the greater segmental mobility of isotactic versus syndiotactic polymethacrylate backbones [246, 247]. 

The monomers XXIV-m-n were crystalline solids and only the monomers with the shortest carbon-segments (n=4) showed an enantiotropic smectic C mesophase. Monomers with higher carbon chains did not exhibit a LC phase. 

Norbornene-based and oxa-norbornene-based monomers bearing dendritic side chains, XXX and XXXI (Fig. 19), were synthesized and polymerized via ROMP with initiator 6 [83]. Based on size exclusion chromatography data, the polymerization shows hving-like character up to DP=70. H- and C-NMR-spectroscopy revealed 35% cis and 65% tram sequences. These polymers displayed enantiotropic nematic and smectic mesophases, except for DP=5. In contrast to other classes of SCLCPs, the dependence of the DP on the transition temperatirre of the polymer was very weak. Glass transition and isotropization temperatures became independent of molecular weight above a degree of polymerization of about 10. 

Enantiotropic SmA mesophases were obtained in mixed heteropolynuclear complexes containing enaminoketone and or7, ti-palladated imine groups 28 transition temperatures and temperature ranges depended strongly on the nature of the enaminoketone derivative. The trinuclear bis(imine) and the tetranuclear chloro-bridged precursory complexes were also mesomorphic, showing an unidentified smectic phase (Cr 118 S 131 I) and a SmA phase (Cr 238 SmA 248 I) respectively. 

Except compound 13 all monomers are enantiotropic liquid crystalline and show nematic or smectic mesophases. Only derivative 13 shows a monotropic s phase. 

The positional order of the molecules within the smectic layers disappears when the smectic B phase is heated to the smectic A phase. Likewise, the one-dimensional positional order of the smectic M phase is lost in the transition to the nematic phase. AH of the transitions given in this example are reversible upon heating and cooling they are therefore enantiotropic. When a given Hquid crystal phase can only be obtained by changing the temperature in one direction (ie, the mesophase occurs below the soHd to isotropic Hquid transition due to supercooling), then it is monotropic. An example of this is the smectic A phase of cholesteryl nonanoate [1182-66-7] (4), which occurs only if the chiral nematic phase is cooled (21). The transitions are aH reversible as long as crystals of the soHd phase do not form. 

Apart from the parent compound 1 and its very simple alkyl derivatives, 1,3,4-oxadiazoles are solids. Solid oxadiazoles containing biphenyl or triphenyl substituents exhibit interesting properties upon heating. The symmetric 2,5-bisbiphenyl-4-yl-l,3,4-oxadiazole 38 melts into an isotropic phase showing small monotropic mesophase. By contrast, the asymmetric (hockey stick-shaped) mesogen 2-terphenyl-4-yl-5-phenyl-l,3,4-oxadiazole 39 exhibits a more stable enantiotropic liquid crystalline phase (a smectic phase as well as a nematic phase) <2001PCB8845>. 

The complexes bearing one chiral substituent display a smectic A mesophase when the non-chiral chain is long, or an enantiotropic cholesteric and a monotropic SmA phase for shorter alkoxy chains. A TGBA phase is observed for the derivative which contains the chiral isocyanide combined with the diethyloxy, when the SmA to cholesteric transition is studied. The compound with two chiral ligands shows a monotropic chiral nematic transition. When this compound is cooled very slowly from the isotropic liquid it exhibits blue phases BP-III, BP-II, and BP-I. 

Ferrocene derivatives 15 exhibited remarkable liquid crystal properties (Fig. 9-13). Indeed, they all gave rise to enantiotropic mesophases. Structures with n = 1 to 11 showed nematic phases. From n = 12 a smectic C phase formed. The latter was monotropic only for 15 (n = 12). The smectic C domain increased from n = 13 to n = 16, and, inversely, the nematic range narrowed. The last member of this series (n = 18) presented one smectic C phase between 159 °C and 179 °C. A nematic to smectic C transition and a focal-conic texture of a smectic C phase are presented in Figs. 9-14 and 9-15, respectively. 

Another interesting phenomenon found by Stevens et al. is the monotropic mesophase formed by the dimer and trimer of the polymer with m = 6. The dimer has a monotropic nematic phase, the trimer has a monotropic smectic phase. These metastable monotropic phases become stable enantiotropic phases with the increase of n by 1. At about the same time, Blumstein et al. (1984) found the low mass model compound of a main-chain type liquid crystalline polymer was monotropic while the mesophase of the polymer was enantiotropic. 

In the meantime, Ohta et studied the complete series of symmetric copper complexes ((53) M = Cu R = R = C H2 +i, = 0 to 14), which confirmed the previous results. The ligand showed a crystal smectic E phase from the octyl derivative onwards as determined by miscibility studies. The first four complexes ((53) M = Cu R = R = C H2 +i, = 0 to 3) were not mesomorphic, then a mono tropic phase was detected for = 4, which became enantiotropic for > 5. Moreover, for n = l and 8, the copper complexes showed an additional mesophase, while the nonyl derivative exhibited two additional mesophases. Crystalline structures of some tetra-alkyl copper, palladium, and nickel complexes of / -diketonates revealed that the flat molecular species were stacked into columns, the planes of the molecules forming a small tilt with respect to the columnar axis-these columns were further organized into layers. Variable-temperature and NMR ... 

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