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.     

Synthesis and mesomorphic behaviors of a series of heterocyclic pyridine-imine-ester based liquid crystals

ABSTRACT

A series of new calamitic liquid crystals, 4-{[(5-methylpyridin-2-yl)imino]methyl}phenyl 4-alkoxybenzoates were synthesized. This series consists of nine members wherein they are differed by the length of alkoxy chain. Spectral analysis results were in accordance with the expected structure. Their thermotropic behaviors were analyzed with Differential Scanning Calorimetry (DSC), Polarizing Optical Microscopy (POM) and powder X-ray diffraction techniques. First member with the shortest alkoxy chain (n?=?2) is a non-mesogen. As the alkoxy chain increased to n?=?4, the monotropic nematic phase appeared. An enantiotropic mesophase (nematic) was observed for the following three members (n?=?6, 8, 10). As the alkoxy chain increased to n?=?12, enantiotropic nematic phase exhibited together with monotropic smectic A (SmA) phase. As the alkoxy chain continuously increased to n?=?14 and 16, enantiotropic phases were observed for both N and SmA. When moving to n?=?18, the nematic phase disappeared and this compound only exhibited a single mesophase (SmA).     

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.     

On some liquid crystalline phases exhibited by compounds made of bent-core molecules and their mixtures with rod-like molecules

In most homologous series of compounds made of bent-core (BC) molecules, the B₂ B₁ and B₆ phases occur as the chain length decreases. We have studied binary mixtures of the compound 1,3-phenylene bis[4-(3-methylbenzoyloxy)]4-n-dodecylbiphenyl 4’-carboxylate (BC12) which exhibits the B₂ phase with the compound 4-biphenylyl 4’-n-undecyloxybenzoate (BO11) made of rod-like (R) molecules. We find the above sequence of occurrence of the B phases with increasing concentration of BOH. In this paper we describe the physical origin for the formation of these phases in both pure compounds and in the mixtures. We have also found the occurrence of the biaxial smectic A phase when the BO11 concentration is increased to 87–95.5 mol%. We also report on another binary system composed of BC12 and 4-n-octyloxy 4’- cyanobiphenyl (8OCB) made of R molecules. This system exhibits the biaxial smectic A phase down to 30°C. Using polarized infrared spectroscopy we find that the mutual orientation of the R and BC molecules in the SmA_db liquid crystal is such that the arrow axes of the BC molecules are along the layer normal of the partial bilayer smectic structure formed by the rods. We also describe unusual growth patterns obtained when the nematic phase transforms to the SmA_db phase in a mixture with 24 mol% of BC12.     

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.     

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.     

Azo substituted V-shaped liquid crystalline compounds: synthesis and mesophase characterisation

The first examples of V-shaped liquid crystalline materials made of non-symmetrical molecules are reported. They belong to a homologous series of azo substituted compounds, wherein the two arms attached to the 1,2-positions of the benzene ring are different. The new compounds are characterised by the spectroscopic methods. The liquid crystalline properties are investigated using polarising optical microscopy, differential scanning calorimetry and X-ray diffraction studies. All the compounds synthesised here are found to be liquid crystalline. They exhibit nematic and smectic A mesophases, which are uniaxial in nature. The preliminary qualitative experiments showed that the compounds are photosensitive. Based on the X-ray results, the molecular arrangement of these compounds in their mesophases is illustrated. A relationship between molecular structures to mesomorphic properties in such systems has also been predicted.     

Synthesis,characterization and mesomorphic behaviour of lanthanide (III) 4-alkoxybenzoates

The lanthanide (III) 4-alkoxybenzoates [Ln(C_nH_2n?+?1OC₆H₄CO₂)₃, Ln?=?La (III), Pr (III), Nd (III), Eu (III), Gd (III), Tb (III) and Dy (III) and n?=?6, 8, 10, 12 and 16] have been synthesized and characterized by elemental analyses, magnetic susceptibility measurements, and IR and electronic spectroscopy. Hot-stage polarizing optical microscopy and differential scanning calorimetry have been used to investigate the mesomorphic behaviour. The chain length influences the structure and hence the thermal behaviour of these compounds. All the lanthanide complexes except decyloxy derivatives exhibit smectic A mesophase. The decyloxy-containing complexes are non-mesomorphic. The differential scanning calorimeter traces do not display the exothermic peak for all the compounds except for the hexadecyloxy derivatives, which exhibit enantiotropic smectic A phase. The influence of the lanthanide ions on the phase transition has also been clearly demonstrated.     

Syntheses and mesomorphic properties of laterally fluorinatedphenyl isothiocyanatotolanes and their high birefringent mixtures

Syntheses and mesomorphic properties of di-, tri- and tetrafluorosubstituted 4′-(4-alkylphenyl)-4-isothiocyanatotolanes are described. Four fluorine substituted compounds in the position 2′, 3′, 3, and 5 show stronger nematic character than difluorosubstituted ones in the position 3, 5 or 2′, 3′. Example of high birefringence nematic mixture and its properties are given.     

Phase behaviors of binary mixtures composed of banana-shaped and calamitic mesogens

In this work, five mixtures with different concentrations of banana-shaped and calamitic compounds have been prepared and subsequently studied by polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction on non-oriented samples. The phase sequences and molecular parameters of the binary systems are presented.     

Layer thinning transition in an achiral four-ring hockey stick shaped liquid crystal

Depolarized reflected light microscopy and high resolution optical reflectivity measurements have been conducted on free-standing films of an achiral four-ring hockey stick shaped liquid crystal exhibiting SmA-B2–SmX* transition sequence. A layer thinning transition above the bulk isotropic-SmA phase transition has been observed. This behaviour was highly irreproducible, indicating an irregular layer thinning transition. From optical reflectivity data, both thickness of the free-standing films and the smectic interlayer spacing were determined. This is the first report of the layer thinning transition in a hockey stick shaped liquid crystal.     

Dielectric spectroscopy of the SmQ* phase

Liquid crystal possessing two biphenyl moieties in the molecular core and lateral chlorine substitution far from the chiral chain has been studied by dielectric spectroscopy. On cooling from the isotropic phase, the material possesses the frustrated smectic Q* (SmQ*) and SmC_A* phases. It has been confirmed by dielectric spectroscopy that the SmQ* phase can be related to the SmC_A* anti-ferroelectric phase. However, only one relaxation process has been observed in the SmQ* phase, while in the SmC_A*, two relaxations are clearly detectable. It seems that the mode found in the SmQ* can be connected with high-frequency anti-phase mode observed in the SmC_A* phase. Its relaxation frequency is similar to P_H relaxation frequency, but is weaker. The same relaxation has been observed even a few degrees above the SmQ*–Iso phase transition. Another explanation for the mode detected in SmQ* and isotropic phases can be molecular motions around short molecular axis.     

High pressure investigations on hydrous magnesium silicate-phase A using first principles calculations: H---H repulsion and changes in hydrogen bond geometry with compression

We have carried out first principles structural relaxation calculations on the hydrous magnesium silicate phase A (Mg₇Si₂O₈(OH)₆) under high pressures. Our results show that phase A does not undergo any phase transition up to ～45 GPa. We find that non-bonded H---H distance reaches a limiting value of 1.85 Å at about 45 GPa. The hydrogen bond bending mechanism for countering the H---H repulsive strain that was proposed by Hofmeister et al. for phase B is not the only one operating in phase A. It also has contributions based on the reduction of one of the O–H bond distances and opening up of the H---O---H angle with compression. The contraction of the O–H distance with pressure, perhaps the first one by density function theory calculations, will have implications for the spectroscopic measurements.     

Effect of defects and surface anchoring on the phase behavior of chiral smectic liquid crystals

The influence of defects and surface effects on the stability of phenomena accompanying phase transitions, mainly coexistence phenomenon, has been studied. Experimental measurements were carried out by varying the cell thickness and using simple experimental on chiral smectic liquid crystal product. The analysis of the results with different cell thickness leads us to interpret the anomaly shown by our product related to impact of defects and surface effects. Moreover, the phase transition is affected by the trace of defects for thick cell and by the surface effect for thin cell. These effects have the same role as an electric local field which can induce phase transition.     

Ab initio study of the structure,cooperativity, and vibrational properties of HNC ternary complexes with two HF molecules

MP2/aug-cc-pVDZ calculations have been used to provide information on the three ternary systems comprising one HNC and two HF molecules. The binding distances, frequency shifts, and interaction energies in these systems have been analysed to study the cooperativity of hydrogen bond in these systems. The cooperativity of hydrogen bond in HNC–HF–HF trimer is larger than that in HF–HF–HNC trimer. The result indicates that the proton acceptor HNC plays a more important role in enhancing the cooperativity of hydrogen bond. Many-body interaction analyses have also been performed for these ternary systems.     

Synthesis and thermoelectric properties of Mn-doped AgSbTe2 compounds

Polycrystalline p-type Ag 0.9 Sb 1.1 x Mn x Te 2.05（x = 0.05,0.10,and 0.20） compounds have been prepared by a combined process of melt-quenching and spark plasma sintering.The sample composition of Ag 0.9 Sb 1.1 x Mn x Te 2.05 has been specially designed in order to achieve the doping effect by replacing part of Sb with Mn and to present the uniformly dispersed Ag 2 Te phase in the matrix by adding insufficient Te,which is beneficial for optimizing the electrical transport properties and enhancing the phonon scattering effect.All the samples have the NaCl-type structure according to our X-ray powder diffraction analysis.After the treatment of spark plasma sintering,only the sample with x = 0.20 has a small amount of MnTe 2 impurities.The thermal analysis indicates that a tiny amount of Ag 2 Te phase exists in all these samples.The presence of the MnTe 2 impurity with high resistance and high thermal conductivity leads to the deteriorative thermoelectric performance of the sample with x = 0.20 due to the decreased electrical transport properties and the increased thermal conductivity.In contrast,the sample with x = 0.10 exhibits enhanced thermoeletric properties due to the Mn-doping effect.A dimensionless thermoelectric figure of merit of 1.2 is attained for the sample with x = 0.10 at 573 K,showing promising thermoelectric properties in the medium temperature range.     

光子晶体的相位特性在高灵敏温度传感器中的应用

对含耦合缺陷的不对称结构光子晶体的研究发现,其缺陷模频率附近的反射率接近于1,而缺陷模频率附近反射光的相移随频率迅速改变;当缺陷层为折射率的温度敏感材料时,温度的极微小变化就能使处于缺陷模频率的反射光相移发生很显著变化.根据这一原理,设计了高灵敏高分辨率的相位温度传感器.以高灵敏高分辨率的温度传感器为例,介绍高灵敏高分辨率的相位传感器的工作原理. 关键词： 光子晶体 相位 传感器     

Electro-optical Kerr effect in the isotropic phase of the two antiferroelectric liquid crystal mixtures

We have experimentally studied for the first time the electro-optical Kerr effect and the pre-transitional behavior in the isotropic phase of two antiferroelectric liquid crystal mixtures, W-232 and W-204D, composed of rod-like ester molecules exhibiting the direct smectic-A to isotropic (SmA-I) phase transition. The Kerr law has been confirmed for the two compounds and the variation of inverse Kerr constant with temperature above the smectic–isotropic transition temperatures were determined. Both the mixtures with very broad antiferroelectric phase around room temperature have similar sequence of the phases (i.e., Cr-SmC*A-SmC*-SmA-I). Although, the pre-transitional behavior is usually complex in the isotropic phase of the chiral smectic liquid crystal compounds, the investigated compounds showed a similar behavior compared to that of nematic–isotropic behavior.     

Phase transition,structural, mechanical and thermal properties of erbium pnictides under pressure

In this article, we have investigated the high-pressure structural phase transition of erbium pnictides (ErX; X?=?N, P and As). An extended interaction potential model has been developed (including the zero-point energy effect in three-body interaction potential model). Phase transition pressures are associated with a sudden collapse in volume. The phase transition pressures and associated volume collapses have been predicted successfully. The elastic constants, their combinations and pressure derivatives are also reported. The pressure behaviour of elastic constants, bulk modulus and shear modulus have been presented and discussed. Moreover, the thermophysical properties such as molecular force constant (f), infrared absorption frequency (υ ₀), Debye temperature (θ _D) and Grunneisen parameter (γ) have also been predicted.     

Electro-optical properties of nanodispersions based on ferroelectric thiobenzoates

The influence of differential nanoparticles on the properties of ferroelectric liquid crystal based on chiral thiobenzoates series was investigated by optical and electro-optical methods. MHOBS4/ZnO, MHOBS4/Ag and MHOBS10/SWCN nanocomponents were prepared. A small addition of nanoparticles leads to changes in electro-optical properties. This is due probably to the various mutual arrangements of nanoparticles and liquid crystal molecules.