Photochemical E-Z isomerization reaction in the series of chiral 1R,4R-2-arylidene-p-menthanone derivatives has been studied and the behavior of starting materials and photoproducts in liquid crystalline systems was characterized. The differences in photochemical properties of the studied compounds with several benzene rings in arylidene fragments and those containing ester linking groups were revealed and discussed.
New chiral compounds 3R-methylcyclohexanone derivatives were synthesized. These compounds were revealed to exhibit the mesomorphic behavior within rather wide temperature ranges. Types of formed mesophases and phase transition temperatures were determined by polarizing microscopy, differential scanning calorimetry and small angle scattering of X-ray. Mesomorphic properties of the new chiral compounds were compared with those for the chiral 2-arylidene derivatives of 3R,6R-3-methyl-6-isopropylcyclohexanone (d-isomenthone) studied earlier. Distinctions between these two types of compounds in an ability to form mesophases and also in twisting properties as chiral dopants in induced cholesteric mesophases are considered.
Macroscopical properties of some induced cholesteric compositions based on 4-pentyl-4'-cyano derivatives of biphenyl and phenylcyclohexane as host phases have been investigated. The series of N-arylidene derivatives of (S)-1-phenylethylamine with varied both rigid moiety of the N-arylidene fragment and terminal substituent was used as chiral dopants. The influence of the chiral dopant molecular structure as well as of physical properties of the host phases used on the helical twisting power, the temperature dependence of the induced helical pitch and the N* mesophase thermal stability has been characterized. It has been concluded that the distinctions in properties of the LC systems containing the OCH2 and COO linking groups are caused by their different conformational states.
New chiral ethers with the 2-arylidene-p-menthan-3-one skeleton have been investigated as components of the induced cholesteric (N*) systems based on 4-pentyl-4'-cyanobiphenyl. A rather high helical twisting power in combination with the weak temperature dependence of the induced helical pitch has been demonstrated for these compounds. The chiral compounds studied containing the terminal oxyalkyl group have been found to increase the thermal stability of N* mesophase. The experimental results obtained have been interpreted basing on the conformational analysis by semi-empirical AM1 and PM3 methods. The significant predominance of gauche-conformers of bent shape for benzyloxy fragment has been found to be the major factor causing the distinctions in the behavior of these chiral dopants in LC host system with respect to their linear analogs containing no ether linking group. The shift of the conformational equilibrium of the chiral ethers towards more anisometric conformers provoked by the orienting effect of the liquid crysalline environment has been assumed.
Some1R,4R-2-(4-phenylbenzylidene)-p-methane-3-one derivatives containing the ether or ester linking group between benzene rings of the arylidene fragment have been studied as chiral dopants in ferroelectric liquid crystal systems based on the eutectic mixture (1:1) of two phenylbenzoate derivatives (see paper for formula) The ferroelectric properties of these compositions (spontaneous polarization, rotation, viscosity, smectic tilt angle as well as quantitative characteristics of their concentration dependences) were compared with those for systems including chiral dopants containing no linking group. Ferroelectric parameters of the induced ferroelectric compositions studied have been shown to depend essentially on the presence of the linking group between benzene rings and its nature as well as on the number of the benzene rings in the rigid molecular core of the chiral dopants used. For all ferroelectric liquid crystal systems studied, the influence of the chiral dopants on the thermal stability of N*, SmA and SmC* mesophases has been quantified. The influence of the linking group nature in the dopant molecules on the characteristics of the systems studied is discussed taking into account results of the conformational analysis carried out by the semi-empirical AM1 and PM3 methods.
By X-ray diffraction has been obtained the information concerning molecular structure of three chiral compounds, p- menthane-3-one derivatives, containing biphenyle fragment (Ia, Ib) and OH-group (II). The cinnamoyl group C6H4-CH=C-C=O is non planar in all compounds investigated but to different degrees. A dependence of the non-planarity of this fragment as well as of the cyclohexanone ring flattening on the substituents X and Y nature is discussed.
A novel pair of the E- and Z-isomeric 1R,4R-2-)4- heptyloxyphenyl)-benzylidene-p-menthan-3-ones has been prepared and the influence of distinctions in their molecular geometry on macroscopic properties of liquid crystal systems with the induced supra-molecular helical structure has been studied. The significantly lower helical twisting power of the chiral Z-isomer in comparison with that of E- one has been confirmed in the case of induced cholesteric systems based on 4-pentyl-4-cyanobiphenyl. The phase behavior and ferroelectric characteristics have been investigated for smectic-C* compositions based on the eutectic mixture of the homological 4-hexyloxyphenyl-4'- hexyloxy- and 4-hexyloxyphenyl-4'-octyloxybenzoates containing the novel isomeric chiral dopants. The spontaneous polarization of the opposite signs induced by the isomeric chiral components has been revealed for the compositions studied. Distinctions in phase states, absolute values of the spontaneous polarization, smectic tilt angle and rotation viscosity of the systems obtained are discussed.
Morphology, transmittance and dynamic characteristics of the liquid crystal composites with dispersed polymer and without have been studied. It is found that the introduction of 2 percent of polymer decreases threshold voltages and rise time, increases slope of the voltage-transmittance characteristic and contrast ratio.
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