Temperature columnar discotics

Chains of 8-AOB can be both stiffened and/or projected in off-angle directions when unsaturated groups are introduced. For example, a double bond places a stiff, bent segment along an alkyl chain. The liquid crystalline phase of 8-AOB is lost when an E or Z configuration double bond is placed near a chain middle (between C4 and C5 8(3)-D-AOB), but the clearing temperature - 356.SK for the E isomer and 354 K for the Z isomer, compared to 356.5 K for the saturated (parent) molecule - is affected only slightly [108]. By contrast, placement of the double bond at the ends of the alkanoyloxy chains (8(6)-D-AOB), stabilizes the columnar discotic phase which persists from 306 to 343 K [108]. 

IX Applicable Properties of Columnar Discotic Liquid Crystals s versus Temperature for HAT6... 

Berardi et al. [66] have also investigated the influence of central dipoles in discotic molecules. This system was studied using canonical Monte Carlo simulations at constant density over a range of temperatures for a system of 1000 molecules. Just as in discotic systems with no dipolar interaction, isotropic, nematic and columnar phases are observed, although at the low density studied the columnar phase has cavities within the structure. This effect was discovered in an earlier constant density investigation of the phase behaviour of discotic Gay-Berne molecules and is due to the signiflcant difference between the natural densities of the columnar and nematic phases... 

Fig. 4 Hekates with shape-persistent oligothiophene and oxadiazole arms. Only the endcapped molecules with extended arms revealed LC phases. Colob columnar oblique phase, ND discotic nematic phase. All transition temperatures are given in °C...

Pc macrocycle. Some of them are mesomorphic and show a Colh phase (Fig. 79 I-Gl G 115 Coin 270 I II-Gl G <-20 Colh > 320 h H-G2 G 115 Colh 250 I II-G3 94 Colh 108 I) for which the structure of the columnar mesophase is frozen at room temperature (anisotropic glasses). The functionalization of these dendrons in the 3 and 5 position of the terminal rings by oligo(ethyleneoxy) chains (0CH2CH2)30CH3, and their subsequent grafting onto the phthalocyanine of type I (Fig. 79) led to amphiphiUc materials [333]. In concentrated ethanol solutions ( 20-40% by mass), the compound with the fimctionaUzed G1 dendron behaves as a discotic amphiphUe forming a coliunnar nematic lyotropic phase. In addition, it possesses a columnar mesophase stable from room temperature up to 260 °C. Systems of type III are not mesomorphic. 

Triphenylenes provided with nonionic di(ethylene oxide) side-chains (25f)132 134 or with ionic alkyl chains (25g)135 form supramolecular polymers in water.136 The arene—arene interactions of the aromatic cores allow for the formation of columnar micelles . At low concentrations the columns are relatively short, and the solutions are isotropic. At higher concentrations the longer columns interact and lyotropic mesophases are formed.133 Computer simulations showed that in the isotropic solution the polymerization of the discotics is driven by solute-solute attraction and follows the theory of isodesmic linear aggregation the association constants for dimerization, trimerization, and etc., are equal and the DP of the column thus can easily be tuned by concentration and temperature.137 138 At higher concentrations the sizes of the columns are influenced by their neighbors, the columns align, and the DP rises rapidly. 

The apparent disagreement between simulation results and experimental observations on the the existence of power law relaxation near the isotropic-columnar (I-C) phase boundary needs further attention. This appears to be associated with the existence of nematic-like fluctuations in the experimental system. This can be checked, on the experimental side, by studying the relaxation near the I-C phase boundary located away from the discotic-nematic phase. For simulation, a careful analysis should be done by changing the temperature and density along the phase coexistence line and studying the existence or lack of nematic-like orientational fluctuations. 

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