Synthesis and Mesomorphic Properties of New Columnar Liquid Crystal Containing 1,3,5-triiminebenzene with Pendant 1,3,4-thiadiazole Group

A novel discotic liquid crystal series based on 1,3,5-benzenetrisazomethine derivatives with three pendant 2-amino-5-(4′-n-alkoxy)phenyl-1,3,4-thiadiazole has been synthesized, which is the first columnar molecules containing 1,3,4-thiadiazole moiety exhibiting a discotic liquid crystal. The molecular structure of compounds was confirmed by FT-IR, ¹H-NMR, and mass spectroscopy and elemental analysis. The electron excitation properties of these compounds were investigated by UV-vis absorption spectroscopy. Their liquid crystalline properties were studied by polarizing optical microscopy and differential scanning calorimetry. The formation of a columnar mesophase was found to be dependent on the number of methylene unit in alkoxy side chains.     

Properties of liquid crystals and Cu2+ recognition based on Schiff bases

Two series of new Schiff base compounds were synthesized. For Schiff base compounds with a pyridine nitrogen atom in 4-position (7a–e), their supramolecular hydrogen bonding complexes show good liquid crystal properties. However, no liquid crystal property is observed for 8a–e. Results of theoretical calculations demonstrate that it is the intermolecular hydrogen bond of Schiff base compounds (8a–e) that prevents the formation of supramolecular hydrogen bonding. The Schiff base compounds, with terminal alkoxy chains, can recognize Cu²⁺ selectively with a color change. Nevertheless, others cannot recognize Cu²⁺.     

Structure and magnetism of low-doped monoclinic crystals of (Ga<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>Se<Subscript>3</Subscript>

The influence that doping with Mn³⁺ ions has on the fine crystal structure of the monoclinic compound Ga₂Se₃ was studied by single-crystal neutron diffraction and the measurements of magnetic properties. It was found that the structural state of the crystals changes even at relatively low doping levels (x = 0.04). Local Jahn-Teller distortions were shown to be responsible for the formation of the fine structure and magnetism in this type of compounds.     

Synthesis and mesomorphic behavior of symmetrical chiral liquid crystal dimers incorporating ester linked biphenyl- naphthyl cores and terminal vinyl group

A series of symmetrical chiral, liquid crystal dimeric molecules possessing ester- linked, biphenyl-naphthyl cores with varied spacer lengths and terminal vinyl groups have been synthesized using Naproxen as the synthetic precursor. The synthesized symmetrical chiral dimers were characterized by 1H NMR spectroscopy, and their liquid crystalline behavior was confirmed by DSC and HOPM studies. Structural effects on the mesomorphic and physicochemical properties were investigated in terms of variation of chiral chain length. The synthesized dimeric compounds exhibited SmX^*, SmC^*, SmA^*, N^*, BPI^*, and BPII^* mesophase sequences. An odd-even effect was observed in the dimers and the duration of the mesophase decreased with increasing spacer length. The synthesized vinyl substituted liquid crystalline dimers are particularly useful in understanding liquid crystal polymorphism and act as model compounds for liquid crystal polymers.     

Synthesis and Liquid Crystal Behaviour of Further 4,4″-Disubstituted 2'-Fluoro-1,1':4',1”-Terphenyls

Further to earlier work on the liquid crystal properties of fluoro-1,1':4',1”-terphenyls¹ we have now extended this series to include terminally fluoro-and cyano-substituted 2'-fluoro-1,1':4',1″-terphenyls, chiral 2'-fluoro-1,1':4',1″-terphenyls, and esters derived from 2'-fluoro-1,1':4',1”-terphenyls and incorporating the alkylcyclobutyl group. The preparations and transition temperatures for these series of compounds are presented and their transition temperatures and mesophase types are discussed. An interesting result from this work was the appearance of an S^* _C phase for one chiral homologue and of S _c phases for the esters incorporating the alkylcyclobutyl group. The S _c formation is attributed to the presence of the fluoro-substituent.

Keywords: terphenyls, fluoroterphenyls, smectic C phases, cyclobutyl esters     

Charge Carrier Transport 1n 1:1 Complexes of Tetracyanobenzene with Naphthalene Anthracene and Durene

Abstract

It is well established that crystals of charge transfer (CT) complexes formed between aromatic donors and acceptors are built up of linear stacks of closely packed molecules. There are two main types of CT crystal structure, (i) a parallel arrangement of linear stacks made up of the individual component molecules, AAAA…DDDD… and (ii) a parallel arrangement of linear stacks made up of alternating molecules, ADADA… In each case it is to be expected that the intermolecular forces between the face to face packed molecules in each stack are far greater than those forces between stacks. A considerable anisotropy in physical properties which are a strong function of intermolecular interactions is a natural result of these crystal structures. Such anisotropy has been reported in the few crystals of the ADAD structure which have been examined, for example, in triplet exciton motion in biphenxl² and anthracene tetracyanobenzene (TCNB) complexes³,⁴ and in charge carrier mobilities μ in anthracene⁵ and phenthrene-pyromellitic-acid-dianhydride⁶ as well as anthracene-trinitrobenzene⁷. Carrier mobilities which were reported were all low, < 0.1 cm²/V sec., and though the major interesting questions were posed, such as what is the effect of different donors on μ?; or are there separate conduction and valence bands for acceptors and donors?; the dearth of mobility data on a range of materials leaves these questions unanswered. We have recently measured the mobilities of holes in several TCNB complexes as a first step towards understanding carrier transport in such materials. These are a particularly interesting series of materials in that triplet motion is said to be primarily two dimensional in anthracene TCNB³, and unidimensional in biphenyl TCNB². Since the transport of charge, like triplet exciton motion, is dominated by exchange interactions, and since CT triplet     

1,2-Dithiolene complexes of transition metals-structural systematics and physical properties

The crystal structure analyses along with other physical measurements of 1,2-dithiolene complexes have made it possible to derive many interesting properties of these complexes. This review focuses attention mainly on the structural aspects and physical properties of 1,2-dithiolene complexes of transition metals. Brief mention of the structural aspects of complexes such as 1,2-dithiooxalate complexes and dithiosquarate complexes is included. In addition, structural aspects of a few available non-transition metal complexes are briefly discussed. The idea that bulky counterions lead to nonplanar structures has been disproved by the nonplanarity observed in the anion of [(CH₃)₄N]₂[Cu(S₂C₂(CN)₂)₂]. The analysis of the significance of overall charge shows that the ionic effect is prevalent in [M(dithiolene)₂] ^n– systems. Crystal structure analyses of some bis(dithiolene) complexes of transition metals along with conductivity measurements have shown that it is possible to correlate the electrical behavior to the crystal structure, provided the sample crystals are good. The two-dimensional network structure of the mixed valence compound, [(n-C₄H₉)₄N]_0.29 [Ni(S₂C₂S₂CS)₂], proposes the possibility of reaching the ultimate goal (superconductivity) with this type of compounds.     

Chemical Bond in AIIBV2 Systems from Magnetic Susceptibility Data

Some peculiarites of chemical bond in A^IIB^V₂ systems from the data on the magnetic susceptibility of the A^IIB^V₂ compounds and their solid solutions are discussed. With this aim in view the magnetic susceptibility has been divided into the Langevin diamagnetic and van Vleck paramagnetic terms. The diamagnetic susceptibility of valence electrons, affecting the chemical bond in a crystal against the covalency parameter along the A – B, A – A, B –B bonds in A^IIB^V₂ compounds, has been analysed. The covalency parameter of the A^IIB^V₂ compounds has been evaluated. Closeness of the covalency parameter values for monoclinic β-ZnP₂ and tetragonal CdP₂, CdAs₂, is evidently, one of the reasons for the solid solution formation between the above mentioned compounds.     

Synthesis and characterization of some novel liquid crystalline compounds of 1,3,4-oxadiazoline and their hydrazone derivatives

Three new series of mesogens have been synthesized by fixing 4-methoxy or 4-butoxy substituted phenyl ring in one side and 4-hydroxy, bromo or amino substituted phenyl group in the other side with different central linkage. The molecular structure of these series was confirmed by elemental analysis and FTIR and ¹HNMR spectroscopy. The mesomorphic properties were studied by using differential scanning calorimetry (DSC) and optical polarizing microscopy (OPM). All the compounds of series [I] exhibit enantiotropic smectic B (SmB) phase. All the compounds of series [II] and [III] display SmB and nematic (N) phases. The mesomorphic properties were found to be dependent on the two terminal 4-substituted phenyl groups and the central linkage group.     

Behaviour of Ultrasonic Velocity in Cholesteric Liquid Crystals

Ultrasonic velocities (V) have been determined, employing a fixed path double crystal interferometer, in three cholesteric liquid crystals, namely cholesteryl propionate, cholesteryl laurate and cholesteryl myristate in their isotropic and anisotropic phases including the region of the phase transition. The variation of specific volume (v) is also studied in the same temperature range by a special dilatometer constructed for this purpose. Anomalous behaviour of ultrasonic velocity is observed near the isotropic-cholesteric phase transition in all three compounds. In the two polymesomorphic liquid crystals, namely cholesteryl laurate and cholesteryl myristate, contrary to the ultrasonic behaviour of cholesteryl stearate, prominent velocity dips are observed at cholesteric-smectic transition temperatures. The parameters adiabatic compressibility (β_ad) and molar sound velocity (R) are estimated and they are found to exhibit sudden jumps at cholesteric-smectic and isotropic-cholesteric transitions. The thermal expansion and temperature co-efficient of compressibility are found to show abnormal increase near the phase transition indicating the existence of large-magnitude pre-transitional effects near the phase transition. A comparative study of the ultrasonic behaviour of six aliphatic esters of cholesterol has shown that the magnitude of the velocity dip observed at the isotropic-cholesteric transition increased with increase of molecular weight and only cholesteryl acetate shows deviation.     

Liquid Crystal Compounds Incorporating the Trans-1,4-Substituted Cyclohexane Ring System

A number of esters and other compounds containing a trans-1,4-substituted cyclohexane ring system-have been prepared, and the liquid crystal thermal stabilities of these new mesogens are discussed in relation to those of their analogues containing the 1,4-phenylene ring. The observed effects are discussed in terms of a possible thermal energy absorption by the cyclohexane ring in causing minor conformational changes.

Other physical properties of these new mesogens are also discussed with particular reference to their potential in applications. In relation to electro-optical display devices, such properties as birefringence, dielectric anistropy, viscosity etc., are important parameters, and the new materials have been assessed in this context as possible additives to the 4-n-alkyl- and 4-n-alkyloxy-4′-cyanobiphenyls for producing a favorable combination of physical parameters.

Also reported is a liquid crystal mixture which has a 100°C nematic range and which contains only materials which are aliphatic. This mixture is assessed for its potential application as an anistropic solvent in analytical techniques such as ultra-violet spectroscopy and nuclear magnetic resonance spectroscopy.     

High-Pressure X-ray Diffraction Studies on Organic Crystals

The high-pressure X-ray diffraction technique, commonly applied for inorganic crystals, is discussed in a view of its application for laboratory studies on molecular crystals of organic compounds – particularly when the weak X-ray scattering of such specimens causes experimental difficulties. To minimize the background-to-signal ratio, relatively big crystal samples (ca. 0.005 A³) were used and the mechanical properties of the gasket material were applied to obtain the optimum experimental conditions for pressure generation and lowering the background of reflections. The mechanical properties of tungsten, Inconel, and hardened steel gaskets are different and these properties can be helpful in planning high-pressure measurements with large high-pressure chamber to contain a big crystal sample. Several characteristic features of organic crystals – like their strong compressibility (depending on the nature of intermolecular interactions) and pressure-dependence of thermal vibrations of atoms – can have a direct impact on the conditions of high-pressure experiments. The properties of molecular crystals of organic compounds have been discussed on the basis of several high-pressure structural studies, mainly on simple cyclic β-diketoalkanes (enol forms). It has been attempted to assess the feasibility of investigating the details of molecular structure at high pressures by X-ray laboratory studies. A systematic pressure-induced change in the length of double C  O bonds is observed in this group of compounds, which can be correlated with the compression of the H-bonds involving the carbonyl groups.     

Relationship between the rotation angles of octahedra and bond-strength energy in crystals with perovskite structure

The dependence of the strain energy of anion-cation bonds on the sum Ψ² of squares of the angles of ordered rotations of octahedra around the coordinate axes of the reduced cell has been determined for ABX ₃ compounds with perovskite structure in the two-particle approximation. A relation determining the change in the thermodynamic Gibbs potential with allowance for the change in the bond-strain energy in the dependence on Ψ² is proposed. An expression for the equilibrium value of Ψ² as a function of the bond-strain energy and temperature is obtained. Analysis of Ψ² is performed for a homologous series of LnVO₃, LnFeO₃, and LnAlO₃ compounds (Ln are rare earth elements) and a series of CaBO ₃ and SrBO₃ compounds has been performed. It is shown that the calculated values of Ψ² for each of these series of compounds are in agreement with the values experimentally obtained from the structural data. The transition temperatures of the compounds belonging to the series studied into the cubic phase are estimated and compared with the experimental data.     

Synthesis, atomic structure, and properties of crystals in the RbTiOPO4-CsTiPO5 system

The subsolidus region of the phase diagram of the RbTiOPO₄-CsTiPO₅ system has been studied in the temperature range 700–1000°C, and the boundaries between the stability fields of the orthorhombic phase with the KTiOPO₄-type structure and the cubic phase with the pyrochlore-type structure have been determined. Single crystals of the RbTiOPO₄ and CsTiPO₅ based solid solutions were synthesized by crystallization from flux. The crystal structure and the physical properties of the first members of the series were studied.     

Efficient and practical method for the synthesis of hydrophobic azines as liquid crystalline materials

A series of hydrophobic symmetrical azines: 1,2-bis[4-(n-alkoxy)benzylidene]hydrazine (where, n-alkoxy: O(CH₂)_nH, n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 16, or 18) have been prepared following an efficient and practical method. These compounds have been synthesized via the condensation reaction of hydrazine hydrate and appropriately 4-(n-alkoxy) benzaldehydes in acidic medium under ambient conditions. The prepared organic compounds have been characterized and their structures were elucidated depending upon micro-elemental analysis and spectral data (IR, UV-Vis, ¹HNMR, ¹³C{¹H}NMR, 2D ¹H-¹H-cozy, 2D ¹H-¹³C-HSQC, and mass spectra). Liquid crystalline behavior of the prepared compounds was studied using polarized light optical microscopy and differential scanning calorimetry techniques. This study revealed that all the compounds displayed enantiotropic liquid crystal properties, exhibiting smectic and nematic mesophases.     

Synthesis and mesomorphic properties of 2,4-bis(4′-n-pentyloxybenzoyloxy)- benzylidine-4″- n-alkoxyaniline

The synthesis and mesomorphic properties of a new series of 2,4-bis(4′-npentyloxybenzoyloxy)- benzylidine-4″ -n-alkoxyaniline (DC5An) are reported. The molecular structure of compounds was confirmed by FTIR, ¹H-NMR, ¹³C-NMR, mass spectroscopy and elemental analysis. The mesomorphic properties were studied by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) measurements. All compounds of the series exhibit nematic (N) and smectic C (SmC) phases. The first four homologues (DC5A1-DC5A4) display a N mesophase, whereas the highest homologues (DC5A5-DC5A10) exhibit an enantiotropic dimorphism N and SmC phases. The mesomorphic properties of the present series are compared and discussed with other structurally related series.     

Phase transition and thermal stability of reentrant smectic phase in mixture of liquid crystalline materials

In the present work, our investigation is to study the optical and thermal properties of the binary mixture of cholesteric and nematic compounds namely, decyloxy benzoic acid (DBA), and cholesteryl chloride (ChCl), which exhibits different liquid crystalline phases with reentrant smectic-A phase. The reentrant smectic-A phase has been observed at different concentrations and at different temperatures. The existence of reentrant smectic-A phase has been observed by optical microscopic studies. The temperature variation of optical anisotropy, X-ray and helical pitch of the cholesteric (N^*) phase has also been discussed.     

Study of Y-shaped liquid crystalline materials with polar nitro substituent

A new homologous series of Y-shaped liquid crystals namely 4-Nitro-[2′4′bis (4″-n-alkoxybenzoyloxy)] phenyl bisazobenzenes have been synthesized and its thermotropic properties studied on the hot stage of a polarizing microscope. The compounds consist four phenyl rings joined through ester and bisazo linkages with alkoxy and nitro as terminal substituents. The structures of synthesized compounds were confirmed by spectroscopic techniques such as FTIR, ¹HNMR as well as elemental analysis. The compounds were found to exhibit enantiotropic nematic and smectic mesophases. The role of molecular shape, size and polarity of functional groups in the mesophases formation is discussed.     

Study of relation between liquid crystal properties and molecular structure of halogenated benzyl alcohol ester derivative

Comparison among the structurally similar analogous or isomeric novel homologous series of presently investigation is discussed with a view to understand the effect and relation between molecular structure in respect of molecular size, geometrical shape, molecular polarity and polarizability etc as emerged from changing molecular rigidity and flexibility which is played by terminal or central bridge to inducing liquid crystal property and the specific degree of mesomorphism of a substance. Novel series of study consists of three phenyl rings, two central bridges ?COO?, ?CH?CH?COO?, ?COO?CH₂?, ?CH?CH?COO?CH₂? with common left n-alkoxy (?O?C_nH_{2n + 1}) left terminal group which vary from homologue to homologue in the same series and varying tail end group –Cl and –Br. Novel members of series were selectively characterized and confirmed by elemental analysis, IR spectra, H¹NMR spectra, mass spectra, POM, textures of smectic or/and nematic phase by miscibility method etc. Totally 66 novel compounds were synthesized and 55 compounds were to be found liquid crystal (LC) in nature with different degree of mesomorphism depending upon changing molecular structure in respect of their tailed flexible end groups or central bridges.     

3-Aryloxypropiononitriles Intermediates: Crystal and Molecular Structure of 2- and 4-(2-Bromoethoxy)diphenylmethanes

The crystal structure of 2- and 4-(2-bromoethoxy)diphenylmethanes ( I and II respectively), intermediates in a novel synthesis of substituted 3-aryloxypropiononitriles, have been determined by single crystal X-ray diffraction at room temperature (r.t.) and at 150K. No significant changes in the crystal structure of I and II have been observed in going from r.t. to 150K. In both compounds the bromoethoxy group presents a gauche conformation and shows a short Br.O intramolecular interaction that allows to explain the very good reaction yields obtained in the novel synthesis. The three-dimensional structure of I is stabilized by two intermolecular hydrogen bonds and that of II by six. This difference in the crystal packing of I and II explains the variation in the m.p. The analysis of ¹H and ¹³C NMR spectra suggests that the molecular conformations in solution are similar to those found in solid state.