Structural,dielectric and conductivity behaviours of cetyltrimethylammonium bromide/ethylene glycol-based quenched lyotropic mesophases

The present study highlights the effect of quenching on the structural, textural and dielectric dynamics of cetyltrimethylammonium bromide/ethylene glycol binary mixtures of varying concentrations 30:70, 50:50 and 75:25 wt.%. No mesomorphism is seen in the as-prepared binary mixtures as X-ray diffraction and polarisation optical microscopy studies reveal the crystalline-like structures for the studied concentrations. With the effect of quenching, lyotropic hexagonal phase is obtained at 30:70, 50:50 wt.% concentration; however, mixture with higher 75:25 wt.% concentrations exhibit crystalline-like phase. The obtained hexagonal lyotropic phases restrain the mesomorphism up to ≈340 K and then show crystalline-like structures with the further increase in the temperature. Dielectric and relaxation behaviours of hexagonal lyotropic phases are presented in this study. The relaxation parameters of lyotropic phases are also discussed. Interestingly, the hexagonal lyotropic phases obtained for 30:70 and 50:50 wt.% concentrations exhibit ac conductivity of the order of 10^–5 S/m, which can be seen as a significant result of this study.     

Enhancement of the stability and temperature range of the mesophases in the binary mixtures of cholesteryl myristate and 4-n-decyloxy benzoic acid

Thermodynamical, optical, and electrical properties of the binary mixtures of cholesteryl myristate (ChM) and 4-n-decyloxybenzoic acid (DOBA) have been carried out by the differential scanning calorimeter, polarized optical microscopy (POM), and impedance spectroscopy. Through thermodynamic study, various phase transition temperatures, transition enthalpies, and transition entropies have been determined to investigate temperature range and stability of the mesophases of the mixtures. Phase diagrams in the heating and cooling cycles have been drawn for the ChM–DOBA binary system. Optical textures of different mesophases have identified with the help of POM. Dielectric permittivity has been determined in planar and homeotropic alignments of the mixtures having DOBA concentrations 30.0 and 92.3 mol %. The experimental dielectric data in the frequency range of 1 Hz to 35 MHz do not show any relaxation mode in both the alignments of these mixtures. Dielectric anisotropy has been determined for the various observed phases of the mixtures.     

Liquid crystalline behaviour of hydrogen bonded complexes of a non-mesogenic anil with p-n-alkoxybenzoic acids

Phase diagrams of binary mixtures of the non-mesogenic N -( p -methoxy- o -hydroxybenzylidbe ene)- p -aminopyridine with a series of p - n -alkoxybenzoic acids ranging from methoxy to hexadecyloxy were established using differential scanning calorimetry and polarising optical microscopy. The key results obtained are: (1) the formation of 1 1 hydrogen bonded complexes between the pyridine derivative and the alkoxybenzoic acids, (2) the stability of the alkoxybenzoic acid mesophases over a wide range of compositions (up to slightly over 50 mol% of the pyridine derivative), (3) the absence of additional mesophases corresponding specifically to the 1 1 complexes, and (4) the complete miscibility of the acids with the complexes in the mesomorphic state. With alkoxy chains from methoxy to heptyloxy, mixtures produce only nematic phases; they produce both nematic and smectic phases with chains from octyloxy to dodecyloxy, and only smectic phases with chains from tetradecyloxy to hexadecyloxy. The formation of hydrogen bonded complexes was investigated at various temperatures using FTIR spectroscopy. Molecular ordering was studied by X-ray diffraction as a function of temperature and composition both for the crystalline and the mesomorphic states.     

Structural and dielectric behaviour of non-aqueous lyotropic mixtures: influence of amphiphile chain lengths and counter ions

This study highlights the effects of amphiphile chain length and counter ions on the self-assembly and dielectric behaviour of non-aqueous lyotropic liquid crystals. Two-dimensional hexagonal mesophase is seen for short-chain length sodium dodecyl sulphate, while lamellar and multiwall lamellar mesophases are noticed for long-chain length cetyltrimethylammonium bromide and polyoxyethylene (20) sorbitan monolaurate amphiphiles in the non-aqueous domains of ethylene glycol. A strong influence of amphiphile counter ions is seen on static dielectric constant, loss factor, relaxation frequency and relaxation time of these lyotropic mixtures. Refractive indices of these lyotropic phases are also highlighted.     

Synthesis and mesomorphic behaviour of hexacatenar di-hydrazine derivatives

A new series of hydrazide derivatives of N,N-bis(3,4,5-tris(heptyloxy)benzoyl) (T7 series) were designed and synthesised. Investigations on the liquid crystalline properties by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and polarising optical microscopy (POM) showed that the di-hydrazine derivatives exhibited different mesophases, which were ascribed to the different structure of T7 series. The rectangular columnar mesophases of T7-ben remained stable down to room temperature during cooling, T7-fuma was decomposed at 259°C in the first heating, while T7-mal showed simple cubic mesophase and crystalline phase at room temperature during cooling. Comparing Fourier-transformed infrared (FTIR) at room temperature of T7 series, some differences were found in the N–H stretching vibration and C = O stretching vibration bands, indicating that T7 series had some differences in intermolecular hydrogen bond strength, which were caused by the different linking unit of T7 series. Intermolecular hydrogen bonding between –C = O and –N–H groups in crystalline and liquid crystalline phases was confirmed by temperature FTIR spectroscopy and temperature ¹H NMR spectroscopy.     

Thermal analysis of binary liquid crystalline mixtures

Two series of binary mixtures composed of bent shaped and rod like molecules are reported. The first star shaped bent core molecules were synthesized and used as a component of binary mixtures. The chiral rod like compounds having commensurable length with the arms of the bent core compounds have been chosen for these mixtures. The resulted compositions show various thermotropic liquid crystalline phases that are characteristic to both types of liquid crystalline materials. In case of mixing the rod like molecules to the bent core compound the B2, B7 and induced B1 phases have been observed. While using the star-shaped bent core and chiral rod like compounds in mixture, the paraelectric smectic A, ferroelectric smectic C* and orthogonal hexatic smectic B phases were preferred. The appearing mesophases were investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction methods.     

Structural characterization of organosiloxane liquid crystals with a transverse or longitudinal dipole

In this work we report the characterization of two organosiloxane liquid crystalline compounds by means of DSC, polarizing optical microscopy and X-ray diffraction. These compounds can be used for dye guest-host ferroelectric displays. We focus this investigation on the molecular organization of the SmC phases of the two pure compounds to help elucidate the physical behaviour of mixtures with different concentrations of the dye and the guest host. The existence of longitudinal and transverse dipoles in the molecules of the dye and the chiral guest-host respectively are responsible for the different molecular organizations in the SmC mesophases of each compound. Taking into account the experimental results and the complexity of the molecules, we present coherent models to explain the molecular arrangements in the mesophases of both compounds.     

Structural characterization of organosiloxane liquid crystals with a transverse or longitudinal dipole

In this work we report the characterization of two organosiloxane liquid crystalline compounds by means of DSC, polarizing optical microscopy and X-ray diffraction. These compounds can be used for dye guest-host ferroelectric displays. We focus this investigation on the molecular organization of the SmC phases of the two pure compounds to help elucidate the physical behaviour of mixtures with different concentrations of the dye and the guest host. The existence of longitudinal and transverse dipoles in the molecules of the dye and the chiral guest-host respectively are responsible for the different molecular organizations in the SmC mesophases of each compound. Taking into account the experimental results and the complexity of the molecules, we present coherent models to explain the molecular arrangements in the mesophases of both compounds.     

Effect of a lateral substituent on the mesomorphic properties of ferroelectric side chain liquid crystalline polysiloxanes

The synthesis of side chain liquid crystalline polysiloxanes containing oligooxyethylene spacers and ( S )-2-methylbutyl 4-\[(4-oxybiphenyl-4-yl)carbonyloxy]-3-fluorobenzoate mesogenic side groups is presented. Differential scanning calorimetry, optical polarizing microscopy and X-ray diffraction measurements reveal liquid crystalline properties for all synthesized monomers and polymers. All three precursor olefinic monomers reveal cholesteric and smectic A phases. The olefinic monomer which contains two oligooxyethylene units in the spacer is the only one which reveals a twist grain boundary A phase and a blue phase, besides the cholesteric and smectic A phases. All three polysiloxanes present enantiotropic smectic A and chiral smectic C phases. The mesomorphic behaviours of the monomers and polymers are compared with those of the corresponding monomers and polymers without the lateral fluoro substituent. The results seem to demonstrate that incorporating a lateral fluoro substituent in the mesogenic cores of the monomers affects not only the mesophase thermal stability, but also the nature of the mesophases formed. However, incorporating a lateral fluoro substituent in the mesogenic cores of the polymers affects only the thermal stability of the mesophases formed. The lateral fluoro substituent has a more profound effect on the mesomorphic behaviour for the monomers than that for the polymers.     

Lyotropic liquid‐crystalline behavior of polyisocyanodipeptides

Rigid, helical polyisocyanodipeptides derived from alanine (PIAAs) that form lyotropic liquid‐crystalline (LC) phases in tetrachloroethane are presented. An investigation by optical microscopy between crossed polarizers demonstrated that PIAAs prepared by the polymerization of isocyanodipeptide monomers with an activated tetrakis isocyanide nickel(II) catalyst could form cholesteric LC phases in tetrachloroethane in concentrations between 18 and 30 wt %. Cholesteric LC phases that were formed in solutions of greater than 25 wt % displayed a reversal of the cholesteric helix upon annealing at 50 °C. Diastereomeric PIAA mixtures displayed cholesteric LC behavior only when the PIAAs had the same helix screw sense. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 981–988, 2007     

Phase separations in liquid crystal-colloid mixtures

We present a mean-field theory to describe phase separations in mixtures of a nematic liquid crystal and a colloidal particle. The theory takes into account an orientational ordering of liquid crystals and a crystalline ordering of colloidal particles. We calculate phase diagrams on the temperature-concentration plane, depending on interactions between a liquid crystal and a colloidal surface and a coupling between nematic and crystalline ordering. We find various phase separation processes, such as a nematic-crystal phase separation and nematic-isotropic-crystal triple point. Inside binodal curves, we find new unstable and metastable regions which are important in phase ordering dynamics. We also find a stable nematic-crystalline (NC) phase, where colloidal particles dispersed in a nematic phase can form a crystalline structure. The coexistence between two NC phases with different concentrations can be appear though the coupling between nematic and crystalline ordering.     

Synthesis and characterization of luminescent hockey stick‐shaped liquid crystalline compounds

A general synthetic strategy, based on a convergent approach, allowed us to prepare a series of luminescent unsymmetrical bent‐core compounds (2,5‐(disubstituted)‐1,3,4‐oxadiazole derivatives), via the Sonogashira crosscoupling reaction, all possessing a similar hockey stick shape. Their mesophases were characterized using polarizing optical microscopy and differential scanning calorimetry. The observed LC phases possess the classical textures of calamitic liquid crystals. Fluorescence in solution for these compounds exhibits strong blue emission (λ_{max em.} = 390–460 nm) with good quantum yields (50–85%).     

A tilted ferroelectric smectic phase emerging from monomer/polymer mixtures

Mixtures of a fluorescent liquid crystalline side chain polyacrylate and its corresponding ferroelectric monomer were studied by optical microscopy, DSC, X-ray and electro-optic techniques. For some of these mixtures we surprisingly found the emergence of the ferroelectric S*_x phase, which is not exhibited by the single components. The crystalline phase of the monomer is completely suppressed by polymer concentrations above 25 per cent. The 50 per cent polymer-containing mixture shows a clear eutectic effect for the tilted phases and allows electro-optic switching close to room temperature, more than 40 K below the melting point of the monomer.     

Synthesis of luminescent liquid crystals derived from gallic acid containing heterocyclic 1,3,4-oxadiazole

This article describes the synthesis, liquid crystalline and photophysical properties of luminescent liquid crystalline compounds, derived from gallic acid containing heterocyclic 1,3,4-oxadiazole. The mesophases of these compounds were characterised using polarising optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). All compounds showed high thermal stability and blue photoluminescence in solution, with emission maxima between 376 and 381 nm. For all compounds, the liquid crystalline behaviour was preserved on cooling from the isotropic state to room temperature. These characteristics make these materials good candidates for application in organic electronics.     

Driving Forces of the Self-Assembly of Supramolecular Systems: Partially Ordered Mesophases

The main aspects are considered of the self-organization of a new class of liquid crystalline compounds, rigid sector-shaped and cone-shaped dendrons. Theoretical approaches to the self-assembly of different amphiphilic compounds (lipids, bolaamphiphiles, block copolymers, and polyelectrolytes) are described. Particular attention is given to the mesophase structures that emerge during the self-organization of mesophases characterized by intermediate degrees of ordering, e.g., plastic crystals, the rotation-crystalline phase in polymers, ordered and disordered two-dimensional columnar phases, and bicontinuous cubic phases of different symmetry.     

Induced smectic phases in phase diagrams of binary nematic liquid crystal mixtures

To elucidate induced smectic A and smectic B phases in binary nematic liquid crystal mixtures, a generalized thermodynamic model has been developed in the framework of a combined Flory-Huggins free energy for isotropic mixing, Maier-Saupe free energy for orientational ordering, McMillan free energy for smectic ordering, Chandrasekhar-Clark free energy for hexagonal ordering, and phase field free energy for crystal solidification. Although nematic constituents have no smectic phase, the complexation between these constituent liquid crystal molecules in their mixture resulted in a more stable ordered phase such as smectic A or B phases. Various phase transitions of crystal-smectic, smectic-nematic, and nematic-isotropic phases have been determined by minimizing the above combined free energies with respect to each order parameter of these mesophases. By changing the strengths of anisotropic interaction and hexagonal interaction parameters, the present model captures the induced smectic A or smectic B phases of the binary nematic mixtures. Of particular importance is the fact that the calculated phase diagrams show remarkable agreement with the experimental phase diagrams of binary nematic liquid crystal mixtures involving induced smectic A or induced smectic B phase.     

6-Hydroxyhexyl 4-(E)-4-alkoxy/halostyryl)benzoates: synthesis,characterisation and study of mesomorphic and fluorescent properties

Hydroxyhexyl esters of alkoxy and halostilbene carboxylic acids were prepared and studied for thermal, liquid crystalline and fluorescent properties. The decomposition temperatures were determined thermogravimetrically and the compounds were found stable at least up to 200°C. Differential scanning calorimetry (DSC) indicated two mesophases in alkoxystilbene caboxylates. The smectic nature of the liquid crystal (LC) compounds was identified from the optical textures and confirmed through X-ray diffraction (XRD) measurements, where SmA, SmB and CrE mesophases were observed. The compounds 3a-g and 3h-k show single absorption maxima in UV-visible spectra at around 338 and 322 nm, respectively. All the alkoxy compounds emit blue light in solution and in solid state in the wavelength range of 422–425 nm.     

Liquid crystals based on calix[4]arene Schiff bases

New liquid crystals based on calix[4]arene Schiff base were prepared by the reaction of tetraamino-calix[4]arene with aldehydes (4-hydroxy benzaldehyde, 2-vanillin, 4-vanillin and 2-hydroxy naphthaldehyde). Dielectric investigations on a magnetically oriented sample forming N, SmA, and SmC phases were carried out. The dielectric constant (ε’ and ε”) and dielectric loss (tan δ) have been determined as a function of frequency (20 Hz–2 MHz). The synthesized derivatives were purified and characterized by FT-IR, ¹H-NMR, ¹³C-NMR and MALDI-TOF MS. All the synthesized compounds were investigated for liquid crystalline properties using DSC (Differential Scanning Calorimetry), DTA (Differential Thermal Analysis) and POM (Polarizing Optical Microscopy) attached with a hot stage. They generally exhibited nematic and typical fanlike or mosaic texture, which suggest the ordered smectic mesophases. Compounds were found to adopt a specific molecular structure due to the rigid bowl like calix[4]arene core, i.e., a cone-like structure with mesogenic units aligned within the molecule.     

The influence of sodium chloride and urea on chromonic liquid crystals formed by CI Acid Red 266

Chromonic liquid crystals are currently receiving renewed interest with particular attention on the Edicol Sunset Yellow (ESY)/water system, which forms columnar nematic and hexagonal phases. CI Acid red 266 is structurally fairly similar to ESY and also forms columnar nematic and hexagonal phases but at much lower concentrations (>1%). In this study, we have examined the influence of sodium chloride and urea on chromonic liquid crystals formed by CI acid red 266. The techniques employed were polarising microscopy, X-ray diffraction and ²H NMR. Sodium chloride moves the concentration at which mesophases form to higher values. Once formed, the mesophases are stable to slightly higher temperatures. Screening of the interstack electrostatic repulsions by added electrolyte appears to be responsible for the changes. Urea can be added in fairly large concentrations (up to 25 wt%) without significant changes in mesophase stability. X-ray diffraction measurements show that there is little change in the aggregate structure with added urea. NMR measurements on urea and water ordering show that urea has much larger order parameters than water. Both order parameters are much smaller than values reported for ESY, but this is simply because of the lower dye concentrations. The larger order parameters for urea appear to arise from some intercalation of urea into the acid red 266 stacks. There is no evidence for changes in ‘water structure’ by the addition of urea.     

Synthesis and mesomorphic properties of rigid-core ionic liquid crystals

Ionic liquid crystals combine the unique solvent properties of ionic liquids with self-organization found for liquid crystals. We report a detailed analysis of the structure-property relationship of a series of new imidazolium-based liquid crystals with an extended aromatic core. Investigated parameters include length and nature of the tails, the length of the rigid core, the lateral substitution pattern, and the nature of the counterion. Depending on the molecular structure, two mesophases were observed: a bilayered SmA2 phase and the more common monolayered SmA phase, both strongly interdigitated. Most materials show mesophases stable to high temperatures. For some cases, crystallization could be suppressed, and room-temperature liquid crystalline phases were obtained. The mesomorphic properties of several mixtures of ionic liquid crystals were investigated. Many mixtures showed full miscibility and ideal mixing behavior; however, in some instances we observed, surprisingly, complete demixing of the component SmA phases. The ionic liquid crystals and mixtures presented have potential applications, due to their low melting temperatures, wide temperature ranges, and stability with extra ion-doping.