Synthesis and transition temperatures of novel fluorinated chiral liquid crystals containing 1,4-tetrafluorophenylene units

To continue the search for novel series of fluorinated ferroelectric liquid crystals, an additional two series of 4-[(S)-2-methylbutoxy]phenyl 4-[(4-n-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] benzoates (C) and 4-(n-alkoxy)phenyl 4-[(4-(S)-2'-methylbutoxy-2,3,5,6-tetrafluorophenyl)] benzoates (D) have been synthesized. Polarizing microscopic textural observations and DSC measurements of the phase transitions of these novel compounds showed that compounds C were liquid crystals with a chiral nematic (N) phase and a monotropic chiral smectic C phase (S_c), and compounds D exhibited a chiral nematic (N) phase.     

Novel fluorinated liquid crystals. II. The synthesis and phase transitions of a novel type of ferroelectric liquid crystals containing 1,4-tetrafluorophenylene moiety

4-[(S)-2-Methylbutoxycarbonyl]phenyl 4-[(4-n-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl]benzoates have been prepared from the starting material 1-pentafluorophenyl-2-trimethylsilylacetylene. Polarizing microscope textural observation and DSC measurements of the phase transitions of these novel compounds showed that they were liquid crystals with chiral smectic C phase (S*_C), smectic A(S_A) and cholesteric (Ch) phases. The effects of the alkoxy chain length on the transition temperatures and enthalpies were also studied.     

Determination of phase transition temperatures of liquid crystals by a light scattering method

A simple analytical system using light scattering (LS) method has been developed to determine phase transition temperatures of liquid crystals (LCs). Intensity changes of the transmission light through a sample were measured as a function of temperature. All LCs and non-LCs showed appreciable changes in the transmission intensity at the phase transition temperature. The transition temperatures determined by the LS method were identical to those by differential scanning calorimetry (DSC).     

Synthesis and characterisation of benzoxazole-based liquid crystals possessing 3,5-difluorophenyl unit

Series of fluorinated compounds, 2-(3′,5′-difluoro-4′-alkoxybiphenyl-4-yl)-benzoxazole derivatives (nFBx), were prepared and characterised. Their phase transition behaviour was investigated by differential scanning calorimetry and polarising optical microscopy. In the case of carbon atoms in the alkoxy chain between 4 and 10, they exhibited enantiotropic mesophases with the mesophase ranges of 12–119°C and 23–152°C on heating and cooling for compounds bearing different substituents (H, CH₃, Cl, and NO₂). With the exception of nitro-substituted compounds, the nFBx series displayed intense photoluminescence emission at 380–385 nm in methylene chloride solution when they were excited at their absorption maxima. Compared to non-fluorinated analogues, fluorinated compounds nFBx (apart from nitro-substituted compounds) exhibited much lower melting points, but comparable or slightly narrower mesophase ranges during both heating and cooling, which were attributed to the disruption of the side-to-side intermolecular packing caused by the two lateral fluoro substituents.     

Ferrocene-containing liquid crystals bearing a cholesteryl unit

The synthesis and characterization of new liquid crystalline compounds containing ferrocene azo or imino aromatic and cholesteryl units is reported. The purpose of this research was to combine the properties of metals (colour, electronic density, magnetism and polarizability) with those of chiral nematics (high birefringence and presence of physical colours) and correlate relationships between chemical structures and properties in the condensed state.     

Synthesis and properties of new three-ring phenylacetylene liquid crystals containing the cyclohexyl unit

Two series of new three-ring phenylacetylene liquid crystals were synthesized and their physical properties were evaluated. These liquid crystal materials show only a nematic phase, high clearing points and good solubilities. The compounds containing two cyclohexyl rings exhibit moderate birefringence (Δn) values of around 0.14, while those containing one cyclohexyl ring show a broad nematic phase range and high Δn of around 0.33.     

Synthesis and characterization of undecatungstotitanates incorporating a lanthanide or a transition metal

Summary K_n[TiW₁₁M(H₂O)O₃₉]·xH₂)(M=F, Co, Cr, Cu, Mn or Zn) and K₁₃[Ln(TiW₁₁O₃₉)₂]·xH₂O (Ln=a lanthanide) complexes have been prepared and characterized by elemental analysis, by u.v.-vis. and i.r. spectroscopy, by magnetic susceptibility measurements and by thermal measurements.     

Dielectric behaviour of liquid crystals with a pyramidal central unit

Dielectric measurements of oligomeric cyanobiphenyls connected to a pyramid-like central unit are presented. The data are interpreted in terms of the dynamics of the liquid crystalline units. There is no indication of reorientation of the central unit as whole or co-operative effects of piled up central units.     

Amphiphilic carbohydrate-based mesogens incorporating structural features of calamitic liquid crystals

Several examples of liquid-crystalline carbohydrate derivatives incorporating a carbocyclic ring in the side chain are reported and the influence of structural variations discussed. The mesophase observed for all compounds described is smectic A and the mesophase stability is strongly affected by the linking unit between the carbocyclic and carbohydrate moieties.     

Amphiphilic carbohydrate-based mesogens incorporating structural features of calamitic liquid crystals

Abstract

Several examples of liquid-crystalline carbohydrate derivatives incorporating a carbocyclic ring in the side chain are reported and the influence of structural variations discussed. The mesophase observed for all compounds described is smectic A and the mesophase stability is strongly affected by the linking unit between the carbocyclic and carbohydrate moieties.     

Ethylenedioxythiophene as a novel central unit for bent-core liquid crystals

We have discovered that ethylenedioxythiophene (EDOT) can be used as a central unit for the synthesis of bent-core liquid crystals (BC LCs). Two series of EDOT-based BC LCs are prepared via Sonogashira coupling reaction. The mesophase behaviour of all the compounds was characterised using a combination of polarising optical microscopy, differential scanning calorimetry and X-ray diffraction measurements. EDOT-based three-ring compounds were found to be nonliquid crystalline, while all the four derivatives of five-ring series, including a branched alkoxy chain derivative, display enantiotropic nematic phase over wide temperature range. The bent angle of these compounds is about 153°, which falls in between typical rod-like and banana liquid crystals. The transition temperature of branched alkoxy chain compound is lower than straight alkoxy chain compounds. The detailed XRD investigations of all the mesogens corroborate the presence of nematic phase.     

Nematic-isotropic phase transition in lyotropic liquid crystals

We propose a Landau-de Gennes phenomenological model to describe the nematic-isotropic phase transition in lyotropic liquid crystals. The possibility of a first or second order transition is explored by means of the variation of the concentration of surfactant. We show that a Landau point on the nematic-isotropic phase transition line can be achieved under certain conditions. The theoretical predictions are found to be in good qualitative agreement with available experimental results.     

Photochemically induced cholesteric-nematic transition in liquid crystals

By doping a nematic liquid crystal with dissymmetric chiral compounds it has been shown that the twist of the resulting cholesteric structure is proportional to the solute concentration. Using as doping agent a photolabile chiral compound a cholesteric-nematic transition has been obtained under UV irradiation.     

Freedericksz transition in polymeric hexatic liquid crystals

The threshold voltage for the Freedericksz transition of a polymer hexatic liquid crystal depends on the film thickness. This behaviour is attributed to the coupling of the director and the bonds defined by the hexatic order. We fit the results of a simple elastic continuum model to threshold data. The fit is suitable for the estimation of several material constants.     

Nematic-isotropic phase transition in lyotropic liquid crystals

We propose a Landau-de Gennes phenomenological model to describe the nematic-isotropic phase transition in lyotropic liquid crystals. The possibility of a first or second order transition is explored by means of the variation of the concentration of surfactant. We show that a Landau point on the nematic-isotropic phase transition line can be achieved under certain conditions. The theoretical predictions are found to be in good qualitative agreement with available experimental results.     

Synthesis and characterization of thiophene-containing liquid crystals

Six series of liquid crystal materials containing a 2,5-disubstituted thiophene unit were synthesized. The liquid crystal compounds obtained were characterized by NMR, differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction techniques. The properties of liquid crystalline phases were investigated as a function of spacer units, number of aromatic core rings and different terminal moieties. Cyano, methoxy and iodo groups were used as terminal groups. It is found that: (i) compounds having one thiophene ring and one phenyl ring connected by an ester group, with a length/breadth value of 2.1, exhibit no mesophase, while other compounds containing two biphenyl rings, with a length/breadth ratio of 2.7, show mesophases; (ii) the polarity of terminal groups and the flexible spacer length significantly affect the thermal behaviour of these compounds; (iii) the nematic transition range of cyano-containing compounds decreases with increasing length of the flexible spacer, and long alkenyloxy chains tend to facilitate the formation of the smectic phase and suppress the nematic phase in all the mesogenic compounds synthesized.     

The trans-1,4-cyclohexylene group as a structural fragment in liquid crystals

In this review the effect on physico-chemical and electro-optical properties of the introduction of the trans-1,4-cyclohexylene fragment into the molecular core of liquid crystals is discussed, rationalized in terms of existent theories, and compared with the effect of other well-known molecular fragments.     

Rheological properties of chiral liquid crystals possessing a cholesteric-smectic A transition

We have measured the rheological properties of two cholesterol derivatives (cholesteryl myristate and cholesteryl nonanoate) in the vicinity of their cholesteric-smecticA transitions. The results for the two compounds differ qualitatively, and are in agreement with results based on optical observations of new defects in cholesteryl nonanoate showing that this material, traditionally considered as a typical cholesteric, in fact exhibits a TGBA phase between the cholesteric and smectic A phases.