Holmium porphyrin compound liquid crystals: Synthesis and properties

5,10,15,20-Tetra-[(p-alkoxy-m-ethyloxy)phenyl]porphyrin and [5-(p-alkoxy)phenyl-10,15,20-tri-phenyl]porphyrin and their holmium(III) complexes are reported. They display a hexagonal columnar discotic columnar Col(h)) liquid crystal phase and were studied by cyclic voltammetry, surface photovoltage spectroscopy (SPS), electric-field-induced surface photovoltage spectroscopy (EFISPS) and luminescence spectroscopy. Within the accessible potential window, all these compounds exhibit two one-electron reversible redox reactions. Quantum yields of Q band are in the region 0.0045-0.21 at room temperature. The SPS and EFISPS reveal that all the compounds are p-type semiconductors and exhibit photovoltaic response due to pi-pi* electron transitions.

Knotlike chi disclinations in the cholesteric liquid crystals

We investigate the topological properties of N(N >= 1) disclination lines in cholesteric liquid crystals. The topological structure of N disclination lines is obtained with the Hopf index and Brouwer degree. Furthermore, the knotted x disclination loops is proposed with the Hopf invariant. And we consider the stability of such configuration based on the higher order interaction. At last, the evolution of the disclinations is discussed.

Calorimetric study on two biphenyl liquid crystals

The molar heat capacities of the two biphenyl liquid crystals, 3BmFF and 3BmFFXF3, with a purity of 99.7 mol% have been precisely measured by a fully automated precision adiabatic calorimeter in the temperature range between T = 80 and 350 K. Nematic phase-liquid phase transitions were found between T = 297 K and 300 K with a peak temperature of T-peak = (298.071 +/- 0.089) K for 3BmFF, and between T = 316 and 319 K with a peak temperature of T-peak = (315.543 +/- 0.043) K for 3BmFFXF3. The molar enthalpy (Delta(trs)H(m)) and entropy (Delta(trs)S(m)) corresponding to these phase transitions have been determined by means of the analysis of the heat capacity curves, which are (15.261 +/- 0.023) U mol(-1) and (51.202 +/- 0.076) J K-1 mol(-1) for 3BmFF, (31.624 +/- 0.066) kJ mol(-1) and (100.249 +/- 0.212) J K-1 mol(-1) for 3BmFFXF3, respectively. The real melting points (TI) and the ideal melting points (TO) with no impurities of the two compounds have been obtained from the fractional melting method to be (298.056 +/- 0.018) K and (298.165 +/- 0.038) K for 3BmFF, (315.585 +/- 0.043) K and (315.661 +/- 0.044) K for 3BmFFXF3, respectively. In addition, the transitions of these two biphenyl liquid crystals from nematic phase to liquid phase have further been investigated by differential scanning calorimeter (DSC) technique; the repeatability and reliability for these phase transitions were verified. (C) 2004 Elsevier B.V. All rights reserved.

Synthesis and characterisation of novel imidazolium-based ionic liquid crystals with a p-nitroazobenzene moiety

A novel series of compounds with different counter anions, i.e. 1-{[4-(4-nitrophenylazo)phenyloxy]}alkyl-3-methyl-1H-imidazol-3-ium bromide salts (C-n , n=3, 6, 10) and tetrafluoroborate salts (D-n , n=3, 6, 10), were synthesised by the incorporation of an imidazolium group into paraffin side chain-terminated 4-nitroazobenzene derivatives. Their chemical structures were determined by H-1 NMR, C-13 NMR, UV spectroscopy and elemental analysis.

The synthesis and properties of meso-tetra(4-alkylamidophenyl)porphyrin liquid crystals and their Zn complexes

A series of novel, long-chain-substituted, porphyrin derivatives, meso-tetra (4-alkylamidophenyl) porphyrin ligands and their Zn complexes (alkyl = 8,10,12,14,16,18) were prepared by acylation of the amino groups of 5,10,15,20-tetra(4-aminophenyl)porphyrin by alkyl chloride. Mesomorphism was investigated by DSC, polarized optical microscopy (POM) and X-ray diffraction (XRD). Only ligands containing chains > 12 carbon atoms displayed liquid crystalline behaviour, which exhibited a high phase transition temperature and a broad mesophase temperature span, Zn complexes showed no liquid crystalline behaviour. Cyclic voltammetry, luminescence spectra and surface photovoltage spectroscopy revealed that covalent linking of an alkylamido group to the tetraphenylporphyrin molecule influences, significantly, the properties of the porphyrin macrocycle.

SYNTHESIS AND VARIABLE-TEMPERATURE FTIR STUDY OF 5 CHIRAL LIQUID-CRYSTALS INDUCED BY INTERMOLECULAR HYDROGEN-BONDING

Five new chiral liquid crystal systems induced by intermolecular hydrogen bonding between 4-[(S)-2-chloro-3-methyl]butyroyloxy-4'-stilbazole (MBSB, proton acceptor) and 4-alkoxybenzoic acids (nBA, proton donors) were prepared. Their liquid crystalline properties were investigated by DSC and polarized optical microscopy. Chiral nematic and chiral smectic phases were observed, and the thermal stability of one complex was studied through temperature dependent infrared spectroscopy.

SYNTHESIS AND PHASE-BEHAVIOR STUDIES OF 2 NEW CHIRAL LIQUID-CRYSTALS OF SCHIFF-BASE - THE INFLUENCE OF INTRAMOLECULAR HYDROGEN-BOND ON THE PHASE-BEHAVIOR

Two new chiral liquid crystals of schiff-base type have been synthesized. This series of compounds contain a-chloro acidic ester chain prepared from commercially available L-valine. Both of the compounds exhibit tilted smectic phases; their phase transitions were studied using DSC and polarized optical microscopy; the influence of intramolecular hydrogen bonds on the phase behavior was studied as well.

SYNTHESIS OF SOME CHIRAL LIQUID-CRYSTALS AND STUDY OF THE EFFECT OF INTRAMOLECULAR HYDROGEN-BONDING ON THE PHASE-BEHAVIOR

The synthesis of three new series of chiral Schiffs bases containing benzilideneaniline and 2-hydroxybenzilideneaniline moieties as mesogenic cores is presented. Differential scanning calorimetry, optical polarizing microscopy and X-ray diffraction measurements were used to study the phase transition temperatures and behaviour. The results reveal that most of these materials show chiral smectic mesomorphism.

SYNTHESIS OF 2 NEW HYDROGEN-BOND INDUCED LIQUID-CRYSTALS

Two new hydrogen bond induced liquid crystals with 4-butoxy benzoic acid as the proton donor and two chiral substituted stilbazole as the proton acceptor have been synthesized. Their liquid crystal transitions were studied by DSC and optical polarized microscope, the IR spectra of the complexes show the existence of the intermolecular hydrogen bond. The results of DSC and optical polarized microscope show that one of them (4BA-VSZ) has a chiral smectic C phase.

Study of the molecular configuration and the dipole moment in fluorinated liquid crystals

We have investigated the relationship between the molecular configuration and dipole moment of some fluorinated liquid crystals (LCs). The aeornetries of the molecules were preliminarily optimized at empirical AM1 and then were further optimized at B3LYP/6-31G(d) level. The dipole moment has been calculated. It is strongly influenced by the position and number of fluorine substituents in the benzene ring of the molecule. The polarizability, mean polarizabilities, and anisotropic polarizability of the phenylbicyclohexane (PBC) fluorine substituents are also given and discussed. (c) 2004 Wiley Periodicals, Inc.

Studies on the phase diagram of the surfactant/1-pentanol water ternary system II: The liquid crystalline phase

The phase behavior of liquid crystalline in the ternary system of dodecyl dimethyl ammonium hydroxyl propyl sulfonate(DDAHPS)/1-pentanol(C5H11OH)/water deuteron (D2O) has been investigated by polarizing optical microscopy, H-2 NMR spectroscopy methods. The results indicate that two kinds of liquid crystals (the lamellar, and the hexagonal) exist in the liquid crystalline phase region. In this paper, we also use the polarized Raman spectroscopy method to measure the values of the order/disorder parameters and the values of the environment polarity parameters for the samples selected from the liquid crystalline phase region, and compare these two parameters of the samples with those of solid state DDAHPS and liquid state pentan-1-ol.

Studies on the phase behavior of lyotropic liquid crystal in DAD/C4OH/n-C8H18/D2O system

The lytropic liquid crystals in dodecanic acid diethanolamine (DAD)/n-butanol (C4OH)/octane (n-C8H18)/deuteron (D2O) system were studied to determine the phase regions and were investigated by H-2-NMR spectroscopy,optical polarizing microscope and small-angle X-ray diffraction (SAXD) methods. The results indicate that the lamellar, hexagonal and cubic liquid crystals all exist in the above system. Keeping the weight ratio of DAD and C4OH constant,the microphase structure, H-2 quadruple splitting and the interlayer spacing are all changed with the addition of deuteron.

Two-dimensional photonic lattices in polymer-dispersed liquid crystal composites

The relationship between liquid crystal orientational ordering and optical diffraction properties is investigated for a two-dimensional square photonic lattice fabricated in a polymer-dispersed liquid crystal (PDLC) composite. Modifications of the nematic director field in the liquid crystal domains were induced by an external applied voltage and by heating over the nematic-isotropic (N-I) phase transition. They were studied by optical polarization microscopy and by analysing far-field optical diffraction patterns. The intensities of various diffraction orders (from the zeroth up to the eighth diffraction order) were monitored with a CCD camera, and their variations were correlated with the modifications of the director field.

Structure and liquid crystalline properties of 5-[(4 '-heptoxy-4-biphenylyl)carbonyloxy]-1-pentyne

The crystal structure and liquid crystalline properties of a biphenyl-containing acetylene, [5-[(4'-heptoxy-4- biphenylyl) carbonyloxy]-1-pentyne (A3EO7) were investigated by electron crystallography, X-ray diffraction, polarizing optical microscopy, differential scanning calorimetry, transmission electron microscopy, and atomic force microscopy. A3EO7 crystals obtained from a toluene solution adopts a monoclinic P112/m space group with unit cell parameters of a = 6.25 Angstrom, b = 7.82 Angstrom, c = 46.70 Angstrom and gamma = 96.7degrees, as determined using electron diffraction. Upon cooling from the isotropic phase, A3EO7 exhibits a smectic A phase in the temperature range 72.4 - 53.6degreesC. Further lowering of the temperature results in the formation of a smectic C phase which exhibits a strong tendency towards crystallization.

Liquid crystal properties of a mesogenic polyacetylene, poly(11-[(4 '-heptoxy-4-biphenylyl)carbonyloxy]-1-undecyne)

The liquid crystalline properties of a mesogenic poly(1-alkyne) and the corresponding monomer were studied using transmission electron microscopy, X-ray diffraction, polarizing optical microscopy and differential scanning calorimetry. The monomer exhibits a monotropic smectic A phase and a metastable crystalline phase. The rigid polymer backbones do not prevent the mesogenic moieties from packing into smectic A and B phases in the temperature ranges 127.6 - 74.1degreesC and 74.1degreesC - room temperature, respectively, on cooling from the isotropic melt.