Mesomorphism Dependence of Molecular Flexibility with Reference to Bromo Tail Group

Halogenated chalconyl derivatives of novel homologues of esters are synthesized and studied with a view to evaluate their liquid crystal (LC) properties and their dependence on molecular structure with reference to molecular rigidity and flexibility. Novel homologous series of chalconyl esters comprises 12 homologues. All the members of a series are enantiotropically smectogenic. Nematogenic mesophase is missing throughout the series. Textures of smectic phase are of type A or C, as judged either by observing directly the sample homologue through polarizing microscopy or some selected members of the series by miscibility method. Transition temperatures were observed through an optical polarizing microscope equipped with a heating stage. The Cr-Sm transition curve adopts zigzag path and behaves in a normal manner. Sm-I transition curve exhibits an odd-even effect and behaves in a usual established manner. The average thermal stability for smectic is 154.79°C, and the mesogenic phase length range is from 5.1 to 24.4°C. The LC properties of the novel series are compared with structurally similar other known series. Thus, present novel series is fully smectogenic with middle ordered melting type and short range of liquid crystallinity.     

Mesophase behaviour of azobenzene-based angular supramolecular hydrogen-bonded liquid crystals

New types of angular 1:1 hydrogen-bonded supramolecular complexes via hydrogen-bond formation between 4-alkoxyphenylazo benzoic acids (In) and 4-(3?-pyridylazo)-4??-alkoxybenzoates (IIm) with various alkoxy chains (from 6 to 16 carbons) were prepared and investigated for their mesophase behaviour by differential scanning calorimetry (DSC) and polarised-light microscopy (PLM). All prepared homologues were found to be dimorphic, possessing smectic C and nematic mesophases. The formation of 1:1 hydrogen-bonded supramolecular liquid crystals (LCs) complexes was confirmed by FTIR and UV?visible (UV?vis) absorption spectroscopy. The study revealed that nematic transition enhancement (ΔT) decreases with the increase of the alkoxy chain length on the base complement, while it increases with the increase of the chain attached to the acid complement of the complex, that is the stability of the nematic phase is more dependent on the length of the acid component.     

Nematic mesophase enhanced via lateral monofluorine substitution on benzoxazole-liquid crystals

Fluorine is widely used as a lateral substituent to modify the physical properties of liquid crystals. Here, laterally monofluorinated compounds, 2-(4?-alkoxy-2-fluorobiphenyl-4-yl)-benzoxazole derivatives (nPPF(2)Bx) bearing different substituents (H, CH₃, NO₂, coded as nPPF(2)BH, nPPF(2)BM and nPPF(2)BN, respectively) at 5-position, were synthesised and characterised. It is interesting to note that these only display enantiotropic nematic mesophases with mesophase ranges of 12–28°C and 13–45°C on heating and cooling for nPPF(2)BH, 46–97°C and 62–120°C for nPPF(2)BM and 82–108°C and 87–113°C for nPPF(2)BN, which are very different from the corresponding monofluorine-substituted analogue (compounds I) with enantiotropic smectic or smectic/nematic mesophases. The enhanced nematic mesophase is attributed to the reduced π–π interaction/conjugation resulting from the twisted structure of the molecule caused by the introduction of a fluorine atom into the inter-ring of the biphenyl unit. These results suggest that modification of the monofluorine substituent position is an effective method to improve the nematic mesophase in benzoxazole-liquid crystals.     

New mesogenic compounds possessing a biphenyl ester and ether moiety comprising 1,3-dimethylbarbituric acid: synthesis,characterisation and mesomorphic studies

New substituted derivatives of 5-vinyl-1,3-dimethylbarbituric acid were synthesised and evaluated for liquid crystal properties. Two sets of molecules were prepared. One end of all the molecules possesses the 1,3-dimethylbarbituric core. The first set comprises biphenyl ethers, 4a–n and the second set biphenyl esters, 5a–g. Liquid crystalline properties were investigated by POM and DSC techniques. All the compounds exhibited enantiotropic smectic A and nematic mesophases. The LC properties were found to depend on the spacer and terminal alkoxy- chain and alkoxy- ester moiety of the molecules. Smaller alkyl chain members showed a smectic phase, while higher alkyl chain members showed a nematic phase.     

Enlarging the Kerr constant of polymer-stabilised blue phases with a novel chiral monomer

Polymer-stabilised blue phase liquid crystals (PS-BPLC) have attracted many attentions in the area of display and photonic applications because of the superior electro-optical properties. Before application, the problem of high driving voltage should be resolved first. In this report, a new chiral monomer (C5011) has been synthesised and its influence on PS-BPLC was investigated. By adopting this chiral monomer, the Kerr constant of the PS-BPLC could be increased dramatically, which means improved driving capacity can be achieved.     

Self-assembly of thiacyanine dyes in water for the synthesis of active hybrid nanofibres

Water-soluble self-assembled nanostructures were synthesised by simple counter ion exchange of thiacyanine dyes which helps in the formation of nematic (N) and hexagonal (M) chromonic liquid-crystalline (CLCs) phases. Conjugated double bonds as central spacers connected between two benzothiazole segments affect water solubility and liquid crystal formation. Aggregation-dependent properties characterised by ultraviolet–visible, fluorescence and ¹H nuclear magnetic resonance spectroscopy. Sol–gel reaction of dye aggregates with silica species furnishes entangled nanotubular fibres with constant diameter and their length in excess of micrometres, having templates of pore sizes below the mesoporous range. The π–π stacked chromonic aggregate dyes are also of importance in shape selective catalysis, adsorption, desorption micro-patterned materials, and provide a significant step towards biosensor medical applications because of their water-soluble nature.     

Synthesis and physical properties of tolane liquid crystals containing 2,3-difluorophenylene and terminated by a tetrahydropyran moiety

Four series of tolane liquid crystals containing 2,3-difluorophenylene and terminated by a tetrahydropyran (THP) moiety have been synthesised via multistep reactions based on 4-alkylcyclohexanecarboxylic acids and 4-bromo-2,3-difluorophenol. Their properties were measured by differential scanning calorimetry, polarising optical microscopy, Abbe refractometer and an electrical constants instrument. The results show that the THP-based liquid crystals nT reveal a relatively high value of the birefringence, negative dielectric anisotropy, good solubility and a broad nematic mesophase. The effects of the terminal alkyl chain, the lateral fluoro substituents and the THP terminal group on the mesomorphic and physical properties are discussed. Meanwhile, density functional theory calculations of molecular conformation and polarisability were conducted to correlate the experimental findings.     

Quasi-static response and texture evolution of α- and γ-RDX: a comparative study

In this paper, we undertake a comparative study of the stress–strain response and slip activity of α- and γ-polymorph of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) under pressure loading using a rate-dependent single-crystal plasticity model. Texture evolution studies are performed to further understand the effects of the dominant slip systems. The simulations indicate that the difference in elastic moduli and lattice parameters for α- and γ-RDX lead to different elastic–plastic constitutive response in the two polymorphs. γ-RDX exhibits more plastic slip compared to α-RDX for loading on (1 1 1) plane and the two polymorphs have different sets of dominant slip systems. We observe that the high-pressure slip system (0 0 1)[0 1 0] that is determined using molecular dynamics simulations is the most dominant slip system for this orientation. Whereas, for loading on (2 1 0) plane, α-RDX has marginally higher plastic slip than γ-RDX, though the same slip system is dominant for both the polymorphs. The texture evolution for loading on (1 1 1) and (2 1 0) planes follow the path towards the most dominant slip systems for both the polymorphs. We predict that the larger plastic slip in γ-RDX for loading on (1 1 1) plane might play an important role in understanding the reduced sensitivity for shock loading on (1 1 1) plane, when compared to (2 1 0) for which γ-RDX has lesser plastic slip, and (1 0 0) which is purely elastic.