Influence of Lateral Substitution on Mesomorphic Properties of Phenyl 4-Benzoyloxybenzoate Derivatives

A series of liquid crystalline phenyl 4-benzoyloxybenzoates with lateral bromo, cyano or methyl substitutents have been prepared. The effect of these changes on the phase transitions of these compounds is discussed.     

Synthesis and Mesomorphic Behavior of Calamitic Liquid Crystals with a Biphenyl Moiety

A new mesogenic homologous series having a biphenyl moiety has been synthesized by condensing 4-hydroxy-4′-nitrobiphenyl- and methoxy-substituted 4-n-alkoxy cinnamoyl chlorides, and their liquid crystalline properties have been studied. All the members of the series are enantiotropic liquid crystals. The methyl to n-pentyl derivatives exhibit both Smectic A (SmA) and Nematic (N) phases; the higher members, starting with the n-hexyl derivative show only a SmA phase. The plot of transition temperatures versus number of carbon atoms in the alkoxy chain exhibits zig-zag pattern for Sm-N and N-Isotropic (Iso) transition temperature curves. The average thermal stability is compared with other related homologous series. The introduction of polar nitro group increases significant intermolecular force of attraction which stabilizes the molecular orientation. This results into the increase in the thermal stability of the system.     

Orientational order of dissolved molecules in the nematic,smectic A and smectic B phases of 4-n-hexyloxybenzylidene-4′-n-hexylaniline

The orientational order S of a dichroic dye dissolved in a liquid crystal has been determined in the nematic, smectic A and smectic B phase of 4-n-hexyloxybenzylidene-4′-n-hexylaniline. The used method is based on the absorption measurement of unpolarized light in a homeotropic oriented liquid crystalline layer and in an isotropic layer. The orientational order of the dissolved molecules was compared with the order parameter of the liquid crystalline solvent.     

Investigation of the Homologous Series of 4-Propionyl–4′-n-Alkanoyloxyazobenzenes by X-Ray Diffraction

A study of the homologous series of liquid cristalline 4-propionyl-4′-n-alkanoyloxyazobenzenes was performed by x-ray diffraction. Two indipendent parame ters were used, namely the temperature and the paraffinic chain length, in order to obtain some structural in formation. In particular the molecular layer thickness was obtained as a function of the temperature for the different phases and different homologous. A linear de pendence of the molecular layer thickness as a function of chain length was found for the crystalline phase as it was previously observed for the smectic A phase. By comparison of the present data with those of the series 4-acetyl-4′-n-alkanoyloxyazobenzenes, a bilayer molecular organization similar to that of the smectic A phase appears as very probable also for the crystalline phase.     

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.     

Liquid Crystals arrive back home at their birthplace

The preparation and characterisation of a series of hydrogen bonded liquid crystalline dimers containing benzoic acid, alkanoic acid and phenol donors and alkoxy-stilbazole or alkoxy-4-pyridone hydrogen bond acceptors are reported. These heterodimers possess strong intermolecular donor–acceptor hydrogen bonding. The heterodimers, as well some of the individual components used in their preparation, possess liquid crystalline phases.     

Computational analysis of ordering in non-liquid crystalline versus liquid crystalline materials with special reference to <Emphasis Type="Italic">n</Emphasis>BAC

A computational analysis of ordering in non-liquid crystalline p-n-alkyl benzoic acid, having 1 (1BAC), 2 (2BAC) and 3(3BAC) carbon atoms in the alkyl chain has been carried out with respect to translatory and orientational motions, but detailed results are reported only for 3BAC. The evaluation of net atomic charges and dipole moments at each atomic center has been carried out using complete neglect differential overlap (CNDO/2) method. The modified Rayleigh-Schrodinger perturbation theory along with the multicentered-multipole expansion method has been employed to evaluate long-range interactions, while a “6-exp” potential function has been assumed for short-range interactions. On the basis of stacking, in-plane and terminal interaction energy calculations, all possible arrangements of a molecular pair have been considered. A comparative picture of molecular parameters, such as total energy, binding energy, and total dipole moment of 3BAC with higher homologous series liquid crystalline compounds having 4(4BAC), 5(5BAC), and 6(6BAC) alkyl chain carbon atoms, has been given. It is found that, if a suitable functional group is attached to 3BAC, so that the length to breadth ratio is increased, the molecule will show a change in the long-range order, the phase transition temperature and other liquid crystalline properties.     

Contraction of side-on nematic liquid crystalline elastomers micropillars: Influence of molecular parameters

We investigated the structure-property relationship of nematic liquid crystalline elastomer (LCE) actuators obtained from a series of nematic side-on monomers. The liquid crystalline acrylate monomers were designed and synthesized with different tail lengths. Combining a soft lithography technique with photo-polymerization/photo-crosslinking of aligned nematic liquid crystalline monomers and crosslinkers, nematic LCE micropillars were obtained, based on the new monomers. Through microscopic observation, influence of some structural parameters on the thermo-mechanical behavior of the micropillars was investigated. The thermo-mechanical behavior of the LCEs showed a close correlation with to the tail length of the monomer and the spacer length of the crosslinker.     

Supramolecular liquid crystals displaying competitive hydrogen bonding: Small molecule mesogens assembled through different hydrogen bond assemblies

A series of supramolecular assemblies created through competitive hydrogen bonding of a n-alkoxy benzoic acid hydrogen bond donor and a mixture of hydrogen bond acceptors: a liquid crystal-forming rigid bi-pyridyl and a non-mesogenic tetrafunctional pyridyl species. The associative chain structures displayed mesogenic characteristics at loadings dependent on the concentration of the disruptive tetrafunctional agent- systems eliminated liquid crystallinity at 85% inclusion in heating transitions and 90% in cooling. The assembled structures displayed considerable mesophase stability. This was observed through long liquid crystalline lifetimes even at high compositions of 4PD, which generally dampened due to a generalized eutectic effect. It is believed that the freedom of mobility inherent in the C8 Acid allows for the reorganization of the hydrogen bonds in the liquid crystalline state providing for a very high loading of disruptor and long mesophase lifetimes.     

Design,synthesis and liquid crystalline behavior of ethyl 4-((4-alkoxyphenyl)diazenyl)benzoates

A series of ethyl 4-((4-alkoxyphenyl)diazenyl)benzoate is synthesized and the liquid crystalline behavior studied. Synthesized compounds are characterized by FTIR, ¹H-NMR, Mass and single crystal XRD. Differential scanning calorimetry was carried out to study the phase transitions and enthalpy changes. Polarizing optical microscopy revealed the mesogenic properties. These techniques revealed that three compounds (2a, 2b, 2f) exhibit liquid crystalline properties in the range of 80–104°C. POM exhibiting focal conical fan like texture which revealed the presence of smectic phases suggestive of their use in LCD and temperature sensing devices, besides 2c can be used as green emitter in OLEDs.     

Design,Synthesis and Analysis of Chlorohydroquinone Derivatives—Liquid Crystalline Complexes

A novel linear double hydrogen-bonded liquid crystalline material is designed and isolated. The ingredients of the mesogens synthesized are chloro hydroquinone (ClHQ) and p-n alkyloxy benzoic acid (nBAO) where n varied from pentyl to dodecyl alkyloxy carbon numbers. The series is abbreviated as ClHQ + nBAO, and seven of eight synthesized complexes are found to exhibit liquid crystalline phases. These liquid crystalline complexes are characterized by Fourier Transformation Infrared spectroscopy (FTIR) in order to confirm the formation of hydrogen bond. Mesophases and their corresponding transition temperatures are studied by polarizing optical microscopy (POM) and their respective enthalpy values along with the order of the transitions are determined by Differential Scanning Calorimetry (DSC). The experimental measurement of tilt angle is carried out by optical extinction method and fitted to the theoretically predicted mean field exponent which is found to be in good agreement. Dielectric relaxations at different temperatures in nematic phase for the complexes have been carried out and their corresponding activation energy values are calculated from Cole–Davidson plots. Light filtering action in the liquid crystalline complexes is done to validate the commercial applications of these mesogens.     

New liquid crystalline tetrazine derivatives for guest-host displays

A number of new liquid crystalline tetrazine derivatives was synthesized. The electro-optical studies showed that the 3-n-alkyl-6-[4-(4-n-alkyl-cyclohexanoyloxy)phenyl]-1,2,4,5-tetrazines are excellent dyes for guest-host displays with positive colour contrast.     

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 of novel azoester homologous series of liquid crystalline behavior and the study of mesomorphism dependence on lateral substitution of middle phenyl ring

The titled azoester liquid crystalline homologous series consists of eleven homologues. The pentyl to tetradecyl derivatives of the series are nematogenic without exhibition of smectogenic character. Rest of the members of the series are nonliquid crystalline in nature. Textures of the nematic mesophase are schlieren or threaded type. Transition curves in the phase diagram showed normal phase behavior. Transition temperatures and liquid crystal behavior observed under an optical polarizing microscope equipped with a heating stage. An odd even effect is observed for nematic-isotropic transition curve. Analytical and spectral data confirms the structures of the molecules. Present homologous series is predominant nematogenic and partly nonmesogenic. Average thermal stability for nematic is 125.33°C and nematogenic mesophase length varies between 12°C to 48°C at tetradecyl (C₁₄) and octyl (C₈) derivatives, respectively.     

Alkyloxy azo-cinnamate ester based thermotropic liquid crystals and their photophysical investigations

Two series of rod shaped Schiff base containing azo-cinnamate thermotropic liquid crystalline compounds were synthesized and characterized. These molecules have four different alkyl spacers (n = 6, 8, 10, and 12) at one end and a dodecyloxy chain at another end (n = 12) which influence their liquid crystalline properties. Liquid crystallinity commence from six methylene spacer onwards in the series exhibiting with Nematic to Smectic-C mesophases. Analytical data confirm the molecular structures of homologues series of compounds. The characteristic texture of liquid crystalline phases obtained using polarizing‐light microscope with a heating stage. The structural transformation of these liquid crystals was confirmed by differential scanning calorimetry. All the compounds exhibited various calamitic mesophases with wide mesomorphic temperature ranges. The relationship between structure and mesomorphic properties was discussed in framework of geometrical configuration of central unit, linking part, and length of alkoxy chains. Photosensitive azobenzene group undergoes photoisomerization under UV light and monitored by UV-Visible spectroscopy.     

Liquid Crystalline Phases in the Homologous Series of Terephthalylidene-BIS-[4-n-Alkylanilines]

The liquid crystalline polymorphism in the homologous series of terphthalylidene-bis-4-n-alkylanilines was investigated by miscibility experiments. The variants of polymorphism found in the members with carbon atoms n = 3 to n = 10 in the alkyl chains can be derived from a variant HGFICA Nthrough the absence of one or several phases. Beside the known phases H, G, F, C, A, and N, the new phase type 1 was found. The results are discussed in connection with investigations on structure.     

Multirings Aromatic Aldehyde Liquid Crystal with Azo Linkage and Their Photosensitivity in Mesophase

Ten new rod-like aromatic aldehyde liquid crystalline molecules with azo linkage were synthesized, in which bi(trans-cyclohexyl), cyclohexyl phenyl, and biphenyl carboxylic acid mesogenic cores with terminal ethyl, n-propyl, n-butyl, and n-pentyl substituents were esterified with azo benzoic aldehyde. These molecules were designed in an attempt to construct a series of new azo liquid crystalline molecules to investigate the influence of ultraviolet (UV) light on their mesophase. All compounds have been characterized on the basis of their spectral data, differential scanning calorimeter (DSC), and hot stage polarizing optical microscope (HS-POM). All these compounds exhibited liquid crystalline phase that belonged to nematic and photosensitive properties. Their temperature ranges of mesophase are from 101 °C to 150 °C. Under irradiated 365 nm UV light, they showed photosensitivity in the solvent of methanol. Observed under HS-POM, the UV light also did change the textures of these compounds. The result showed that terminal ethyl is enough for these molecules to exhibit wider temperature range of mesophase, and these new molecules have photosensitivities observed under illumination of UV light not only in solution but also in mesophase due to the change of their structures from trans isomer to cis one.     

Synthesis of Novel Ionic Liquid Crystalline Pyrrole Derivatives Having a Viologen Moiety

Abstract

A novel liquid crystalline N-substituted pyrrole having an ionic viologen side chain was synthesized, and was polymerized by a FeCl₃ method. Thermotropic liquid crystalline behavior of the pyrrole and the polymerized material were investigated by DSC, thermo-controlled polarizing optical microscopy, and XRD. The pyrrole derivatives showed two smectic phases between isotropic and crystalline (solid) phases. Viologen functions of redox and cation-radical generation for the pyrrole derivatives were confirmed by cyclic voltammetry with UV-Vis spectroscopy.     

Computer Simulation of Biphenyl-Phenyl Ester Liquid Crystals

Abstract

Molecular orbital (MO) calculation and molecular dynamics (MD) simulation were carried out for a set of smectic liquid crystalline molecules, 8O-O8 (4-octyloxyphenyl-4′-octyloxybi-phenyl-4-carboxylate) and 8O-8 (4-octylphenyl-4′-octyloxybiphenyl-4-carboxylate), to understand the molecular origin of different crystalline structure formation and to predict their conformational property in liquid crystalline phases. The results of MO and MD analyses indicate that the structure of 8O-O8 and 8O-8 in crystalline phase is essentially determined by intramolecular interactions and the experimentally observed structure is chosen as a consequence of intermolecular packing constraints. This paper also reports the first application of two-molecular ab-initio calculation to liquid crystalline systems.     

Biphenyl-based liquid crystal precursors with alkanoate and hydroxyl group

We synthesized a series of 4′-hydroxy-[1,1′-biphenyl]-4-yl alkanoate with a potentially reactive functional hydroxyl group as a LC precursor, which facilitates reaction with other chemical groups to tailor biphenyl-based liquid crystals (LCs) for specific applications. Several liquid crystalline materials were also synthesized based on these LC precursors to show high probability to generate various potential LCs. With increasing chain length, the melting point decreased and R_f (retardation factor: migration distance of substance ÷ migration distance of solvent front) of the synthesized LC precursor increased. This LC precursor series provides a useful first synthesis step to design tunable biphenyl/ester-based LCs.