Study of deviation from normal liquid crystal behavior of mesomorphic-isotropic transition curve in a chalconyl ester series with equipolar terminal end groups

A novel chalconyl ester homologous series RO.C₆H₄.COO.C₆H₄.CO-CH:CH-C₆H₄.OC₈H₁₇(p) synthesized and studied with a view to understanding and establishing the relation between molecular structure and Liquid Crystal (LC) properties of thermotropic mesomorphs. The novel series consists of eleven homologous (C₁ to C₁₆). Enantiotropicnematic type of mesophase formation commences from C₃ homologue and continued up to the last C₁₆ homologue of a novel series. Smectogenic character is totally absent for the novel series. Transition temperatures and the textures of nematic phase were determined through an optical polarizing microscopy (POM) equipped with a heating stage. Textures of nematic phase are threaded or Schlieren. Transition curve Cr-N/I and N-I behaved in normal manner except C₈ homologue which showed negligible deviation from normal behavior. N-I transition curve exhibited odd–even effect. Analytical and structural data supported the molecular structures of homologues. Average thermal stability for nematic is 98.88°C whose degree of mesomorphismvary from 12.0°C to 37.0°C. Evaluated thermometric data of present novel series are compared with structurally similar series. Group efficiency order for nematic on the basis of thermal stability, early commencement of mesophase and the degree of mesomorphism. Thus, present series is predominantly nematogenic and lower middle ordered melting type the low degree of mesomorphism.     

Phase transition behavior and structure of the thermotropic liquid crystal 6‐{[(4′‐{[(undecyl)carbonyl]oxy}biphenyl‐4yl)carbonyl]oxy}‐1‐hexyne

The phase transition behaviors and corresponding structures of 6‐{[(4′‐{[(undecyl)carbonyl]oxy}biphenyl‐4yl)carbonyl]oxy}‐1‐hexyne (A4EE11) were investigated using differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and wide angle X‐ray diffraction (WAXD). In comparison with the published homologues, 5‐{[(4′‐heptoxy‐biphenyl‐4‐yl)carbonyl]oxy}‐1‐pentyne (A3EO7) which shows a monotropic smectic A (SmA) phase and a metastable monotropic smectic C (SmC) phase; 5‐{[(4′‐heptoxy‐biphenyl‐4‐yl)oxy]carbonyl}‐ 1‐pentyne (A3E'O7) that exhibits three enantiotropic stable liquid crystalline (LC) phases, SmA phase, SmC phase and smectic X (SmX) phase; 5‐{[(4′‐heptoxy‐biphenyl‐4‐yl)carbonyl]oxy}‐1‐undecyne (A9EO7) which has a monotropic SmA phase and a metastable crystal phase, A4EE11 integrates the enantiotropy, monotropy and metastability of the LC phases of those three compounds. Upon cooling from isotropic state to room temperature, in the temperature range of 62.0 to 58.5°C, A4EE11 shows an enantiotropic smectic A (SmA) phase with a layer spacing d=32.69Å. Further lowering the temperature, it enters into a metastable monotropic smectic B (SmB) phase with a longer layer spacing d=34.22Å which has a tendency towards crystallization. The metastability of the liquid crystalline phase may associate to the linkage order of the ester bridge between the mesogenic core and the flexible spacer. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dependence of liquid crystallinity on molecular rigidity

A novel homologous series of liquid crystals (LC) of chalconyl derivatives is synthesized and studied with a view to understanding and establishing the effects of molecular structure on liquid crystal properties. The novel series consists of 12 homologues. Nematogenic LC property commences from C₃ and continues up to C₁₄ and the smectogenic mesophase is exhibited from C₄ to C₁₆. The C₃ homologue is a monotropic nematic and the rest of the homologues are enantiotropically smectic and nematic or only smectic (C₁₆). Transition curves Cr-Sm, Sm-N, Cr-I, and N-I behave in normal manner with exhibition of odd-even effect, showing phase behaviors of the series.     

Synthesis,characterization, and mesomorphic investigations of diester-substituted salicylaldimines and their copper (II) complexes

A novel homologous series of N-[4-[4′-n-alkoxy)benzoyloxy-2-hydroxybenzylidene)-4-carbethoxy anilines, H_2n+1C_nOC₆H₄C(O)OC₆H₃(OH)C(H)?NC₆H₄COOC₂H₅ (n = 6, 8, 10, 12, 14, 16) and their copper(II) complexes have been synthesized. All these compounds have been characterized by suitable spectroscopic techniques. The mesomorphic properties of these compounds were investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The ligands exhibit wide range of enantiotropic smectic A and nematic phases as confirmed by their typical optical texture under polarizing microscope. The square planar copper(II) complexes of the ligands show only an isotropic phase at higher temperature and no mesogenic nature is observed. DFT calculations have been performed using GAUSSIAN-03 program at B3LYP level to obtain the stable electronic structure of the ligand with decyloxy chain length and its copper(II) complex.     

In situ composites based on blends of PEEK and thermotropic liquid crystalline polymer

A series of blends were prepared by mixing pellets of the thermotropic liquid crystalline polymers (TLCP) with poly (ether ether ketone)(PEEK) in the dry state under injection mouldingmolding conditions. The mechanical properties of blends were measured, and it is proved that the mechanical properties of blends are better than those of their matrix. Compared with the thermoplastic matrix, the tensile modulus and strength of the blends increased obviously, with the addition of only 2 wt% LCP. At the same time, the addition of TLCP decreased the melt viscosity of the blends.     

Design,synthesis and characterization of hydrogen bonded thermotropic liquid crystals

A homologous series of seven linear hydrogen bonded thermotropic liquid crystals are isolated from p-n-octyloxy benzoic acid (8BAO) and p-n alkyl benzoic acids (nBA, where n varies from 2 to 8). In all the seven complexes, hydrogen bonding is a result of complementary proton-donor and electron-acceptor pairs derived from carboxylic acids of 8BAO and nBA. Spectroscopic characterization such as Fourier Transform Infrared spectroscopy (FTIR) and Nuclear Magnetic Resonance (¹HNMR, ¹³CNMR) are performed for all the seven complexes to confirm the intermolecular hydrogen bonding and the nature of chemical environment respectively. Seven mesogen are examined by Polarizing Optical Microscope (POM) for identification of the phase polymorphism through standard textures. Transition temperatures and corresponding enthalpy values of the individual mesogenic phases are experimentally obtained from the analysis of the respective Differential Scanning Calorimetry (DSC) thermograms. Phase diagram of this homologous series is constructed based on the data of transition temperatures, further qualitative analysis of the phase abundance is discussed. Thermal stability factor for each of the mesogenic phase has been determined. Order of phase transition is experimentally obtained by Navard and Cox technique. Specific heat for each phase transition of individual complexes is derived from the DSC data. Change of color of the texture with temperature in the same phase is referred as parachromatism and is observed in nematic phase of two mesogens.     

Non-display bio-optic applications of liquid crystals

Liquid crystal (LC) devices have been largely developed for LC displays and in the last decade for optical telecommunications; however, their application in the field of optical imaging is just starting to emerge. They can be miniaturised and thus have a great potential to be used with miniature optical imaging systems for biomedical applications. LC devices specifically designed for integration into biomedical optical imaging systems are reviewed. Using a combination of a few LC retarders, spectropolarimetric imaging of tissue can be obtained. LC tunable filters with high dynamic range and large throughput are designed for hyperspectral imaging and for spectral domain optical coherence tomography. The designs are based on several concepts, both using the classical stack of retarders and using more modern designs based on single layer in a Fabry–Perot cavity, in a resonant waveguide structure or in a photonic crystal.     

Imidazolium based ionic liquid crystals: structure,photophysical and thermal behaviour of [Cnmim]Br·xH2O (n = 12, 14; x=0, 1)

The long chain imidazolium halides [C_nmim]Br·xH₂O (n = 10, 12; x = 0, 1) have been synthesized and their structural and thermal behaviour together with their photophysical properties characterized. X‐ray structure analyses of the monohydrates ([C₁₂mim]Br·H₂O: triclinic, P1, no. 2, Z = 2, Pearson code aP112, a = 550.0(5) pm, b = 779.4(5) pm, c = 2296.1(5) pm, α = 81.89(5)°, β = 83.76(5)°, γ = 78.102(5)°, 3523 unique reflections with I_o > 2σ(I_o), R₁ = 0.0263, wR₂ = 0.0652, GooF = 1.037, T = 263(2) K; [C₁₄mim]Br•H₂O: triclinic, P1, no. 2, Z = 12, Pearson code aP11, a = 549.86(8) pm, 782.09(13) pm, c = 2511.3(4) pm, α = 94.86(2)°, β = 94.39(2)°, γ = 101.83(2)°, 2063 unique reflections with I_o > 2σ(I_o), R₁ = 0.0429, wR₂ = 0.0690, GooF = 0.770, T = 293(2) K) show for both compounds similar bilayered structures. Sheets composed of hydrophilic structure regions constituted by positively charged imidazolium head groups, bromide anions and hydrogen bonded water alternate with hydrophobic areas formed by interdigitated long alkyl chains belonging to imidazolium cations with different orientation. Combined differential scanning calorimetry and polarizing optical microscopy shows that the monohydrates as well as the anhydrous imidazolium salts are thermotropic liquid crystals which adopt smectic mesophases. The mesophase region is larger in case of the monohydrates when compared to the anhydrous compounds indicating that water obviously stabilizes the mesophase. All compounds show an intense whitish photoluminescence with short lived (¹π←¹π*) and long lived (¹π←³π*) transitions. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Imaging of bacteria using chromonic liquid crystals

We explored adsorption isotherms of Escherichia coli (E.coli) and Salmonella over the poly-L-lysine (PLL) coated glass surface. The detection of the adsorbed bacteria was explored using 14 wt% di-sodium-chromo-glycate (DSCG) solution in water and 5CB. The textures of the optical cells made up of LCs and the adsorbed bacteria over PLL-coated glass substrate were obtained by using a polarized microscope in the transmission mode under crossed polars. We found that DSCG solution exhibits a dark spot on the adsorbed E.coli and Salmonella. In contrast to DSCG solution, 5CB did not show any dark spot.     

Colloidal structures in confined nematic liquid crystals

Colloidal structures in confined nematics offer novel routes for designing complex optical materials with micrometre and submicrometre functionality. In this paper, we review some of our recently assembled colloidal structures that form in confined nematic cells. We present effective elastic binding via nematic distortion as a mechanism for the assembly of two-dimensional colloidal crystals of elastic dipoles and elastic quadrupoles. We introduce entangled colloids as novel types of structures, where particles are topologically bound by delocalised defect loops, producing robust and possibly chiral structures. The concept of hierarchical assembly is demonstrated in colloids with particles of various scales. In cholesteric blue phases, the assembly of three-dimensional colloidal crystals is shown based on naturally occurring three-dimensional arrays of trapping sites produced by blue phases.     

Modification in dielectric properties of SWCNT doped ferroelectric liquid crystals

Effect of single walled carbon nanotubes (SWCNT) in ferroelectric liquid crystal (FLC) geometry has been studied for low and high concentrations of dopant. The results are compared with the characteristics of pure FLC system. An appreciable change in dielectric permittivity, relaxation behavior and other vital parameters has been observed for SWCNT doped FLC system, which shows the adaptability of carbon nanotubes with that of pure FLC molecule. Under high electric field, highly concentrated SWCNT doped FLC shows enormously large values of dielectric loss. This is due to the high conductivity of SWCNT at higher electric field. Interestingly, such effect is not much prominent for the low concentration of the SWCNT doped FLC system.     

Study of the mesomorphism of benzoates and cinnamates

Two ester homologous series of carboxy (-COO-) and ethylene-carboxy (-CH=CH-COO-) mesogens, viz. α-4-[4’-n-alkoxybenzoyloxy] phenyl β-4’’-methoxy benzoyl ethylenes (1) and α-4-[4’-n-alkoxy cinnamoyloxy phenyl β-4’’-methoxy benzoyl ethylenes (2)] are discussed. Series (1) and (2) differ at their central linking group. Mesophase are observed at four and five number members in both homologue series. Enantiotropic nematogenic property is observed in both series (1) and (2), while some smectic property is exhibited in series (2). Thermal stability of nematic-isotropic in series (1) is relatively low as compared to (2), smectogenic property is totally absent in series (2). In phase diagram, solid-nematic, solid-isotropic, and nematic-isotropic curve follow zigzag path rising and falling. Transition temperatures are observed through hot stage polarizing microscope. Analytical data supports the structure of molecules. Threaded, Schlieren-type textures of homologues are observed through microscope.     

Functionalisation of cholesteric liquid crystals by direct laser writing

Cholesteric liquid crystals selectively reflect circularly polarised light with the same handedness as the helix. Because of their sensitivity to external stimuli, such as heat and electrical fields, various applications utilising their tunability have been proposed. Tuning is usually performed in the bulk, meaning that cholesteric liquid crystals usually possess a single pitch throughout the medium. However, when the helical structure is locally modulated, different optical properties arise, such as tunable photonic defect modes and multiple reflection bands. Here we show a technique to locally modulate the helical structure of cholesteric liquid crystals on a submicron scale, based on two-photon excitation direct laser lithography. Two examples of cholesteric liquid crystal structures with modulated helical structures will be presented.     

Spontaneous homeotropic alignment of nematic liquid crystals induced by a double-armed side chain liquid crystalline polymethacrylate

A liquid crystalline polymethacrylate having two cyclohexylphenyl mesogens on its side-chain (PMG0) was synthesized by the radical polymerization of the corresponding methacrylate monomer (MG0). PMG0 exhibited a smectic A phase around room temperature showing a focalconic fan texture in POM observations and a broad diffusion in a wide angle range of its WAXD profile. Upon slow cooling at ?1 °C min^?1 from the isotropic melt, PMG0 exhibited spontaneous homeotropic alignment between two native glass surfaces. A mixture of the commercial nematic liquid crystal (ZLI-4792) containing 1.0 wt% PMG0 also exhibited a homeotropic alignment, which easily covered hydrophilic surfaces such as glass or polyacrylamide.     

Study of the molecular structure on liquid crystal properties with reference to thermotropic azoester derivatives

An azoester homologues series: RO?C₆H₄?COO?C₁₀H₆?N?N?C₆H₄?OC₅H₁₁ (para) as novel liquid crystalline (LC) materials has been synthesized and studied with a view to understanding and establishing the effects of molecular structure on LC properties with reference to laterally substituted phenyl ring and terminally substituted ?OR and ?OC₅H₁₁ (n) groups; including ?COO? and ?N?N? central bridges. Novel homologous series of thermotropic LC variety consists of thirteen homologues (C₁ to C₁₈). C₁ to C₃ derivatives are nonliquid crystal (NLC); C₄ is only nematogenic and C₅ to C₁₈ are smectogenic plus nematogenic. All the mesogenic homologues (C₄ to C₁₈) are enantiotropically nematogenic or/and smectogenic as confirmed by a polarizing optical microscopy (POM) equipped with a heating stage. Transition curves Cr-I/M, Sm?N, and N?I behaved in normal manner in a phase diagram. Odd-even effect is exhibited by Sm?N and N?I transition curves. Analytical, spectral and thermal data confirms the molecular structure of novel homologues. Novel azoester series is predominantly nematogenic and partly smectogenic whose mesogenic temperatures ranges minimum to maximum from 79.0°C to 162.0°C. Thermal stability for smectic and nematic are 128.2°C and 147.7 °C, respectively. Thus, it is a middle ordered melting type of novel series whose total mesophaselength ranges from 20.0°C to 56.0°C. Textures of nematic are threaded or schlieren and that of smectic are smectic A or C.     

Synthesis of aromatic liquid crystals with asymmetric diester based on rod-like multi-ring system by two-step esterification method

A novel method of two-step esterifications was developed to synthesize compounds with asymmetric double ester groups. By using this method, six rod-like double ester compounds were prepared with p-hydroxy benzaldehyde, p-hydroxy benzoic acid bicyclohexyl carboxylic acid, cyclohexyl benzoic acid and biphenyl carboxylic acid substituted by n-propyl and n-pentyl as main reactants. The structures and properties of target compounds were confirmed by IR, MS, ¹H NMR, elemental analysis, differential scanning calorimetry (DSC) and hot stage polarizing optical microscope (HS-POM). Typical yields of the target molecules were more than 70%. All the molecules have mesophases with the textures of nematic type, indicating a rod-like molecule with a longer rigid skeleton can keep its mesophases. There was no clearing point observed for any of the derivatives before they decomposed so that the temperature ranges of the mesophases could not be determined. The energy differences between frontier molecular orbitals (HOMO-LUMO) (E_g) of the compounds were calculated by cyclic voltammetry (CV). The terminal ring system has an obvious influence on the energy levels and the energy gaps (E_g).     

Monte carlo simulations for blue-phase structure in liquid crystals

Blue-phase liquid crystals form three-dimensional structures in a self-organizing manner and are similar to living tissue structures such as the teeth of mice and collagen tissues. This study presents numerical results regarding the conditions under which blue-phase liquid crystals occur. The Monte Carlo simulations are performed by employing an improved Lennard–Jones potential that considers anisotropy and chirality. The conditions for the formation of the blue phase, which vary with respect to the chirality, are examined first. The relationship between the anisotropic parameters and the chiral parameter for the formation of the blue phase is discussed. Identical blue-phase structures are obtained, even when the cell size and molecular number are varied drastically. This discussion is useful for considering the scale-up problem, which is almost always a difficult issue for molecular-scale simulations.     

Study of mesomorphism and laterally substituted nitro group

A novel thermotropically mesomorphic, meta-substituted nitro group of chalconyl ester series, RO-C₆H₄-COO-C₆H₃-(NO₂)-CO-CH=CH-C₆H₄OC₁₂H₂₅(n) (para) is synthesized and studied with an aim to establish the relation between molecular structure and the mesomorphism with reference to changing molecular flexibility in presence of nitro lateral group. Novel homologous series consist of thirteen homologs (C₁–C₁₈) whose mesomorphism commences from C₅ homolog as enantiotropic nematogenic with absence of smectic property, even in the monotropic condition. Transition temperatures of novel substances were determined by an optical polarizing microscope, equipped with a heating stage (POM). Textures of a nematic phase are threaded or Schlieren. N-I transition curve exhibited narrow, sharp and short odd-even effect; with deviating trend in a phase diagram. Analytical, spectral and thermal data confirmed the molecular structures of homologs. Thermal stability for nematic is 182.89°C, whose mesophase lengths minimum to maximum ranges from 17°C to 45°C and it is an upper middle ordered melting type series. Group efficiency order for nematic is series 1 > series Y > series X, as derived from comparative study of structurally similar analogous series.     

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.