Mesomorphic behaviors of a series of heterocyclic benzothiazole-imine-ester-based liquid crystals

A series of new calamitic liquid crystals, 2-[4-(4-alkoxybenzoyloxy)benzylidenamino]benzothiazoles comprising a heterocyclic (benzothiazole) and two phenyl rings core system, terminal alkoxy chain, imine and ester linkers were prepared and characterized. This series comprises eight members wherein the members vary by the length of alkoxy chain (C_nH_2n+1O-, where n?=?4, 6, 8, 10, 12, 14, 16, 18). Spectral analysis results were in conformity with the expected structure. Their thermotropic behaviors were studied by using differential scanning calorimetry, optical polarizing microscopy and powder X-ray diffraction techniques. A single mesophase (nematic) was observed for the first member of the series (n?=?4). As the alkoxy chain increased to n?=?6, 8, 10, 12, 14, the nematic phase appeared together with an additional SmA phase. When moving from n?=?16 until the highest member (n?=?18), the nematic phase disappeared and these compounds only exhibited a single mesophase (SmA).     

Mesomorphic behaviors of a series of heterocyclic thiophene-imine-ester-based liquid crystals

The synthesis and characterization of a series of heterocyclic liquid crystal, 4-{[(thiophen-2-yl)methylidene]amino}phenyl 4-alkoxybenzoates possessing even number of carbon atoms at the alkoxy chain (C_nH_2n+1O-, n = 6, 8, 10, 12, 14, 16, 18) are reported. The molecular structures of title compounds were elucidated using Fourier-transform infrared spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopic techniques along with mass spectrometric analysis. The phase behavior of these compounds was characterized and studied by differential scanning calorimetry and polarizing optical microscopy. All members exhibited enantiotropic nematic phase except for the highest member (n = 18) which is a non-mesogen. Influence of alkoxy chain length on the transition temperatures of crystal-to-nematic (melting point) and nematic-to-isotropic (clearing point) was studied. Nematic phase range was found to increase from n = 6 to n = 10, then it started to descend from n = 12 to n = 16 and finally the nematic phase disappeared when n changed to 18.     

Synthesis and mesomorphic properties of nonsymmetric liquid crystalline dimers containing azobenzene groups

Four novel nonsymmetric dimers containing azobenzene mesogenic groups were synthesized. The nonsymmetric dimers compounds namely, ethyl 4-[(4-{4-(4-((4-nitrophenyl)diazenyl)phenoxy)alkyloxy}phenyl)diazenyl]benzoate were obtained from the alkylation of ethyl 4-[(4-(4-bromoalkyloxy)phenyl)diazenyl]benzoate with 4-[(4-nitrophenyl)diazenyl]phenol. The mesomorphic properties of the compounds were determined by DSC and polarizing optical microscopy. The first member of the series was nonliquid crystalline while all other homologues display nematic and smectic A phases. The trans-azobenzene groups of the dimers display a high-intensity π–π* transition at about 365 nm and a low-intensity n–π* transition at around 465 nm, therefore, photochromism can be achieved by the introduction of the azo linkage to the dimeric liquid crystalline molecules.     

Synthesis and phase transition behaviours of laterally substituted liquid crystals containing methylhydroquinone: emerging of smectic C phase for higher homologues

A series of laterally substituted low-molar-mass liquid crystals with molecular geometry were constructed with three phenyl rings bridged through ester central groups as the rigid core and a lateral methyl group as the flexible part of a molecule, with a view to understanding and establishing the effect of molecular structure on liquid crystal behaviour. Low-molar-mass mesogens known as 1,4-bis[(4′-n-alkyloxybenzoyl)oxy]toluene with different number of carbon (n) at the alkyl chain have been prepared. Their molecular structures were proposed via physical measurements and spectroscopic techniques. Mesomorphic properties were studied by using differential scanning calorimetry, optical polarizing microscopy and powder X-ray diffraction techniques. The results showed that the melting points as well as the clearing temperatures decreased upon lengthening of the terminal alkyloxy chain lengths. Members with the shorter chain (n = 2–10) exhibited nematic phase. As for higher homologues, members with n = 12, 14, 16 and 18 showed polymorphism, whereby these compounds displayed both smectic and nematic properties.     

Synthesis/structural and mesomorphic properties of substituted hydrazide based calamitic molecules

A set of rod-shaped molecules with central hydrazide moiety has been synthesized and characterized using standard spectroscopic techniques. The thermal behaviors of the final compounds were established by the combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and high-temperature powder X-ray method (XRD). The structure and conformation of the molecules were achieved by FTIR, ¹H NMR, ¹³C NMR spectroscopy and DFT calculations. It is found that two compounds are non-liquid crystalline and two compounds are liquid crystalline (LC). The structure property correlations with alkyl chain, connecting position, hydrogen bonding and without hydrogen bonding were established. The studies envisaged that LC properties are induced due to hydrogen bonding and elongation of the molecular length.     

Birefringence and phase transitions in liquid crystals

The birefringence of liquid-crystalline phases is the result of the parallel order of molecules exhibiting a polarizability anisotropy. The magnitude and sign of the birefringence are determined by the structure and order of the liquid-crystalline phase types as well as by the polarizability properties of the constituent molecules. The characteristic change of the birefringence at phase transitions between liquid-crystalline phases indicates more or less pronounced structural changes. The temperature dependence of the birefringence is due to the temperature change of the molecular order.

It is shown that the structural variety of the liquid crystalline state is reflected by a big variety of their optical anisotropy properties.     

Synthesis and phase-transition behaviors of new symmetrical dimer liquid crystals containing benzothiazole unit

This article reports the synthesis and characterization of a series of homologous symmetrical dimers α,ω-bis[4-(6′-ethoxybenzothiazol-2′-yl)iminomethylphenoxy]alkane. Five members with different lengths of alkyl spacer groups of even parity varying from butyl (C₄H₈) to dodecyl (C₁₂H₂₄) were synthesized. Spectroscopic analysis (IR, ¹H and ¹³C NMR) along with electron-ionization mass spectrometric techniques were employed to verify the molecular structures of the dimers. Differential scanning calorimeter was used for determination of the phase-transition temperature and associated enthalpy changes. Optical studies and mesophase identification were carried out using a polarizing optical microscope attached to hotstage. A diversity of phase-transition behavior was observed as the length of the alkyl spacer increased from C₄H₈ to C₁₂H₂₄. Almost all title compounds exhibited nematic phase except the dimer containing butyl spacer in which the mesomorphic property was absent.     

A model of crack based on dislocations in smectic A liquid crystals

A plastic crack model for smectic A liquid crystals under longitudinal shear is suggested. The solution of the screw dislocation in smectic A is the key to the correct result that we obtained by overcoming a longstanding puzzle. We further use the dislocation pile-up principle and the singular integral equation method to construct the solution of the crack in the phase. From the solution, we can determine the size of the plastic zone at the crack tip and the crack tip opening （tearing） displacement, which are the parameters relevant to the local stability/instability of materials. Our results may be useful for developing soft-matter mechanics.     

Synthesis and phase transition studies on non-symmetric liquid crystal dimers: N-(4-(n-(4-(benzothiazol-2-yl)phenoxy)alkyloxy)-benzylidene)-4-chloroanilines

A new series of non-symmetric liquid crystal dimers N-(4-(n-(4-(benzothiazol-2-yl)phenoxy)alkyloxy)benzylidene)-4-chloroaniline containing benzothiazole and benzylideneimine units connected by a flexible alkyl spacer, –(CH₂) _n –, with n ranging from 4 to 12 in even parity have been prepared. All five members of this homologous series exhibit an enantiotropic nematic phase. The compounds with greater n of 8–12 exhibit both nematic and smectic phases upon cooling. A notable feature among this series is that for the member with n?=?10, the smectic–nematic transition is also present. The nematic–isotropic transition temperatures and associated entropy changes with respect to all compounds in this series exhibit a dramatic dependence on the length of the flexible spacer. A comparison of the transitional properties of this series with those of α-(4-benzylidenechloroaniline-4′-oxy)-ω-[4-(thiophene-2-carboxyl)benzylideneaniline-4′-oxy]alkanes reveals that replacing benzothiazole moiety at one side of the flexible alkyl spacer reduces the nematic–isotropic transition temperature.     

Extension of the resonant scattering technique to liquid crystals without resonant element

We report X-ray resonant scattering experiments performed on the prototype liquid-crystalline compound MHPOBC doped with a chemical probe containing a resonant atom (selenium). We determined directly for the first time the microscopic 3- and 4-layer structure of the ferrielectric subphases ( SmC_FI1^* and SmC_FI2^*) present in MHPOBC. Despite the low fraction of the selenium probe, the resonant signal is strong enough to allow an unambiguous determination of the basic structure of the ferrielectric subphases. These experiments demonstrate that the resonant scattering technique can be extended to liquid crystalline materials without resonant element and may stimulate new studies. A non-resonant Bragg reflection was also found in the SmC_FI1^* phase in pure MHPOBC, consistent with the 3-layer distorted model, but never detected before.     

Hydrazide‐based non‐symmetric liquid crystal dimers: synthesis and mesomorphic behavior

Hydrazide‐based non‐symmetric liquid crystal dimers were synthesized. The liquid crystalline properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and powder X‐ray diffraction (XRD). These non‐symmetric liquid crystal dimers are evidenced to display the monolayer smectic C phase. The effects of the lateral intermolecular hydrogen bonding as well as the length of the terminal alkyl chains and the spacers on the mesophase are discussed. Our studies reveal that intermolecular hydrogen bonding between the hydrazide groups and microsegregation effect is the driving force for the formation of the monolayer smectic C structure. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of fluorination of molecular rigid core in liquid crystal biphenyl benzoate based homologous series

Liquid crystalline perfluorinated biphenyl benzoates were synthesized and investigated. A highly tilted, neat orthoconic smectic antiferroelectric phase was observed. A homologous series of compounds without and with a single fluorine atom substituted at different positions of a molecular rigid core was investigated by standard methods. Influence of fluorine substitution on physical properties of antiferroelectric smectic phase was discussed as well as influence of fluorination on molecular dipole moment orientation and its value were presented. Decrease in rotational viscosity as a result of fluorine substitution within a molecular rigid core was ascribed to changes of molecular packing.     

Mesogenic Schiff base esters with benzothiazole core: synthesis and phase transition studies

A series of new rod-shaped mesomorphic compounds, 6-ethoxy-2-(4-alkanoyloxybenzylidenamino)benzothiazoles, consisting of a 2,6-disubstituted benzothiazole core and a Schiff base central linkage, were synthesized and their structures were ascertained via elemental analysis and spectroscopic techniques. Their mesomorphic properties were studied using differential scanning calorimetry (DSC), polarized optical microscopy (POM) and X-ray diffraction (XRD) analysis. All compounds showed enantiotropic mesomorphism. Whilst the lower members of the series, hexanoyloxy and octanoyloxy derivatives exhibited nematic phase, the higher members (decanoyloxy, dodecanoyloxy, tetradecanoyloxy, hexadecanoyloxy and octadecanoyloxy derivatives) exhibited nematic and smectic C phases.     

液晶表面物理——挠曲电效应研究及进展

向列液晶的“挠曲电效应”在1969年由Meyer首先提出,30年后这一理论才被重视.文章回顾了挠曲电效应的研究历程,总结了已取得的成果,并就挠曲电研究中的基础问题、研究进展、研究现状及存在的问题进行了系统的介绍,为从事此方面研究的工作者提供参考.     

Anchoring transitions of nematic liquid crystals

A crystalline substrate such as mica or gypsum can orient a thin layer of nematic liquid crystal spread on top. By adsorbing one or more other kinds of molecules onto the surface, we have observed transitions in the orientation of the molecules on the surface. These “anchoring transitions” are analyzed via Landau-Ginzburg theory and may be first or second-order. The second-order anchoring transition is the first two-dimensional system where critical fluctuations may be observed optically.     

Technical aspects of dielectric spectroscopy measurements of liquid crystals

The dielectric spectroscopy measurements were performed for antiferroelectric liquid crystalline mixture. For this purpose, the cells with ITO electrodes were prepared. It was found that it is not possible to detect some important relaxation modes in Sm A^*, Sm C^*, and Sm CA^* phases. The own cell mode (related to cell properties, i.e., capacity and resistivity) covers the dielectric response of liquid crystalline medium. Dielectric measurements in cells with gold electrodes were done to show all possible relaxations in antiferroelectric liquid crystals (LCs).     

Convection in relatively thin layers of nematic liquid crystals

Laser-induced convective motion in thin layers (less than a millimeter) of nematic liquid crystals is investigated experimentally. It is shown that convection arising in the presence of the vertical gradient of temperature is toroidal. Velocities of convective motions in the liquid crystal are measured for two different diameters of the incident laser beam. Comparison is made of the threshold of the temperature gradient of convective motions obtained by theoretical estimations and with use of experimental parameters.     

向列相液晶中空间光孤子的观测

分别以He-Ne激光器、半导体激光器和Ar⁺激光器作为光源照射液晶材料，在低光强入射的情况下均观察到了光束的自聚焦现象以及空间光孤子的形成，观察到了长度l>5mm的孤子波和多模空间光孤子，并对空间孤子的产生条件及特性进行了讨论. 关键词： 自聚焦 空间光孤子 向列相液晶     

Comparison of optical compensations based on discotic liquid crystals with linear and non-linear orientation for wide viewing angle twisted nematic liquid crystal displays

Optical compensation film using discotic liquid crystals has been commercialized to suppress light leakage of twisted nematic (TN) liquid crystal (LC) cells in the dark state when the viewing directions are off-axes. In the conventional film, the tilt angle variation of the discotic LC layers is linear, whereas that of the rod-like LC layers in the TN cell is non-linear with twist alignment. We investigated the optical compensation effects in terms of iso-contrast ratio, gray scale inversion and color shift with linear and non-linear orientation in a tilt angle or twist and non-twist orientation on TN-LC cells. The results showed that the optical compensation with non-linear orientation exhibited an improved performance in suppressing light leakage in the dark state.     

Molecularengineering of discotic nematic liquid crystals

Connecting two columnar phase forming discotic mesogens via a short rigid spacer leads to the formation of a π-conjugated discotic dimer snowing discotic nematic (N _D) phase. Attaching branched-alkyl chains directly to the core in hexaalkynylbenzene resulted in the stabilisation of N_D phase at ambient temperature. Pentalkynylbenzene derivatives possessing a combination of normal- and branched-alkoxy chains display a very broad N_D, phase which is stable well below and above the room temperature.