New liquid crystal compounds ( )-4-[5-(2-Methylbutyl)-1,3-dioxan-2-yl]phenyl 4-alkoxybenzoate

New liquid crystal compounds, (+)-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl] phenyl 4-alkoxybenzoates (5), were synthesized. The mesomorphic behaviour of these compounds is compared with that of (+)-4-(5-alkyl-1,3-dioxan-2-yl)-phenyl 4-(2-methylbutoxy)benzoates (6). While compounds 6 exhibited a chiral smectic C phase, the corresponding compounds 5 did not. This might mean that for the appearance of a chiral smectic C phase in these types of compounds, it is necessary that the carbonyl and the chiral groups exist at nearby positions. Transition temperatures to those isotropic state for compounds 5 were lower than those for compounds 6. This result is common in both cases of (+)-4-alkoxycarbonylphenyl-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl]benzoates (7), and (+)-4-(2-methylbutoxy-carbonyl)phenyl 4-(5-alkyl-1,3-dioxan-2-yl)-benzoates (8).     

The mesomorphic anomaly of 4-[2-(4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-pentylcyclohexyl-1-carboxylates

Four homologous series of 4-[2-[4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-alkylcyclohexyl-1-carboxylates have been prepared. Their liquid crystalline behaviour was investigated by optical polarizing microscopy and DSC. Series A, B and C exhibit the nematic phase. The phase transition behaviour of series D is anomalous. The compounds of series D with a short alkoxy chain exhibit enantiotropic smectic A and nematic phases, while those with a long alkoxy chain exhibit only the nematic phase.     

The mesomorphic anomaly of 4-[2-(4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-pentylcyclohexyl-1-carboxylates

Four homologous series of 4-[2-[4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-alkylcyclohexyl-1-carboxylates have been prepared. Their liquid crystalline behaviour was investigated by optical polarizing microscopy and DSC. Series A, B and C exhibit the nematic phase. The phase transition behaviour of series D is anomalous. The compounds of series D with a short alkoxy chain exhibit enantiotropic smectic A and nematic phases, while those with a long alkoxy chain exhibit only the nematic phase.     

Synthesis and antiallergy activity of [1,3,4]thiadiazolo[3,2-a]-1,2,3-triazolo[4,5-d]pyrimidin-9(3H)-one derivatives. II. 6-Alkyl- and 6-cycloalkylalkyl derivatives.

A series of 6-alkyl- or 6-(cycloalkylalkyl)-[1,3,4]thiadiazolo[3,2- a]-1,2,3-triazolo[4,5-d]pyrimidin-9(3H)-ones 1b--o was synthesized from the corresponding 1,3,4-thiadiazol-5-amines 3b--o and the antiallergic activities of the products were evaluated. Among the compounds 6-(2-cyclohexylethyl)- [1,3,4]thiadiazolo[3,2-a]-1,2,3-triazolo[4,5-d]pyrimidin-9(3H)-one 1h, whose X-ray crystallographic stereostructure is shown, was found to be a promising new antiallergic agent, which has low toxicity and dual activity as a leukotriene D4 receptor antagonist and as an orally active mast cell stabilizer.     

The synthesis of [1,2,3]-triazole-based bent core liquid crystals via microwave-mediated ‘Click Reaction’ and their mesomorphic behaviour

A series of [1,2,3]-triazole-based liquid crystal compounds were synthesised via a fast and efficient microwave-mediated ‘Click Reaction’ and their phase behaviour is presented. Most of the 1,4-diaryl-[1,2,3]-triazole compounds exhibited a nematic phase with broad temperature ranges and relatively low transition temperatures compared to previously examined materials. Structural variations, involving regio-isomers and lateral halogenation, gave rise to different phase behaviour of the two families of triazole-based compounds.     

New 1,3-dioxan-type ionic liquid crystal compounds having a large dielectric constant

New pyridinium-type thermotropic ionic liquid crystal materials having a 1,3-dioxan ring in its central core: N-substituted-4-(5-alkyl-1,3-dioxan-2-yl)pyridinium bromides (6) were synthesized. The mesomorphic behaviour of these compounds and dielectric constant perpendicular to the molecular axis were measured. The principal features of these compounds are that they exhibit a smectic A phase over a wide temperature range including room temperature - for example 6f: g -9 SmA 181 I (°C)-and they have a large dielectric constant perpendicular to the molecular axis.     

Synthesis and phase behaviour of a homologous series of polymethacrylate-based side-chain liquid crystal polymers

The homologous series of side chain liquid crystal polymers, the poly[ω-(4-methoxyazobenzene-4′-oxy)alkyl methacrylate]s, has been prepared in which the length of the flexible alkyl spacer has been varied from 3 to 11 methylene units. All the polymers exhibit liquid crystalline behaviour. The propyl and butyl members show exclusively nematic behaviour. The pentyl, hexyl, octyl and decyl members show a nematic and a smectic A phase while the heptyl, nonyl and undecyl homologues exhibit only a smectic A phase. The smectic A phase has been studied using X-ray diffraction and assigned as a smectic A₁ phase in which the side chains are fully overlapped and the backbones are confined to lie between the smectic layers. For the nonyl member an incommensurate smectic phase is observed. The dependence of the transition temperatures on the length of the flexible spacer is understood in terms of the average shapes of the side chains.     

Competition between micro-segregation and anti-parallel alignment of an amphiphilic rod-like liquid crystal

Recently, we reported that a rod-like molecule, 4-[4-(7-hydroxyheptyloxy)phenyl]-1-(4-hexylphenyl)-2,3-difluorobenzene, exhibited a nematic phase with a layered structure and smectic C phases consisting of three states. We prepared a homologous series of the rod-like molecules in which a 2,3-difluoro-1,4-diphenylbenzene unit and a hydroxyl unit are connected via a flexible methylene spacer. We investigated their physical properties using polarised optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). Although they showed nematic, smectic A and smectic C phases, the phase structures were found to depend on the flexible spacer length. Those compounds possessing a shorter spacer length than a heptyl unit exhibited bilayered smectic A and smectic C phases, whereas those possessing a longer spacer length than a heptyl unit showed conventional monolayered smectic A and smectic C phases. A nematic phase with a smectic-like layer ordering was observed for the compound possessing an octyl unit. The structure–property relations of the amphiphilic compounds are discussed.     

Flexible taper-shaped liquid crystal trimer exhibiting a modulated smectic phase

We prepared some taper-shaped liquid-crystalline trimers in which two phenylpyrimidine units and a 1,4-diphenyl-2,3-difluorobenzene unit are connected to 2,4-dihdroxy benzoic acid via flexible spacers. We then investigated their liquid-crystalline properties using polarised optical microscopy, differential scanning microscopy and X-ray diffraction. 6-[4–(5-Octylpyrimidin-2-yl)phenyloxy]hexyl 2-{7-{4-[4–(4-hexylphenyl)-2,3-difluorophenyl]phenyloxy}heptanoyloxy}-4-{6-[4–(5-octylpyrimidin-2-yl)phenyloxy]hexyloxy}benzoate (1) was found to exhibit a phase sequence of isotropic liquid – nematic – intercalated smectic A – intercalated anticlinic smectic C – modulated smectic C. The structure–property relation in the taper-shaped trimers reveals that the modulated phase is induced by competition between an intercalated structure stabilised by dipole–dipole interaction and a monolayer structure by packing entropy effects. Conformational change of compound 1 induced by intermolecular interactions plays an important role in the phase transition behaviour.     

Mesophase behaviour of binary mixtures of bent-core and calamitic compounds

The mesophase behaviour of binary mixtures of bent-core and calamitic liquid crystals is presented. The nematogenic 4,6-dichloro-1,3-phenylene bis[4′-(10-undecen-1-yloxy)-1,1′-biphenyl-4-carboxylate] (I) was the banana-shaped component. As the calamitic compound ethyl 4′-(9-decen-1-yloxy)-1,1′-biphenyl-4-carboxylate (II), similar to one arm of the bent-core molecule, was used which exhibits smectic phases in a wide temperature range. A total of six mixtures with different compositions were prepared and studied by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction on non-oriented samples. In the mixtures, a nematic phase is not concomitant with smectic A phase, and the temperature range of both phases highly depends on the concentration of the comprising compounds. Lowered melting temperatures have been observed for all mixtures with respect to that of the pure compounds. Unforeseen finding is the induction of a monotropic SmC phase in mixtures with lowest concentration of the bent-core compound. Semi-empirical quantum-chemical calculations have also been performed. Based on the calculated molecular conformation, as well as on collected X-ray diffraction data, a model for a possible self-assembly of the banana-shaped and calamitic compounds is proposed.     

Regioselective synthesis of 1-(2,6-dichloro-4-trifluoromethylphenyl)- 4-alkyl-1H-[1,2,3]-triazoles

A new and efficient method for the synthesis of 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-alkyl-1H-[1,2,3]-triazoles by the room temperature 1,3-dipolar cycloaddition of (2-azido-1,3-dichloro-5-trifluoromethyl)benzene with terminal alkynes in the presence of Cu (I) salt as catalyst is reported. All the reactions gave 1,4-disubstituted products with high regioselectivity, as no 1,5-disubstituted product was formed. The structures of all the title compounds have been confirmed by elemental analysis, 1H- and 13C-NMR and in addition, the structure of compound 5a was investigated by X-ray crystallography.     

New 1,3-dioxan-type ionic liquid crystal compounds having a large dielectric constant

New pyridinium-type thermotropic ionic liquid crystal materials having a 1,3-dioxan ring in its central core: N-substituted-4-(5-alkyl-1,3-dioxan-2-yl)pyridinium bromides (6) were synthesized. The mesomorphic behaviour of these compounds and dielectric constant perpendicular to the molecular axis were measured. The principal features of these compounds are that they exhibit a smectic A phase over a wide temperature range including room temperature - for example 6f: g -9 SmA 181 I (°C)-and they have a large dielectric constant perpendicular to the molecular axis.     

Binary mixtures of smectic A1S with abnormal behaviour

Binary mixtures are composed of compounds belonging to the 4'cyanobiphenyl-4-yl 4'-n -alkylbiphenyl-4 carboxylate homologous series and halogenophenyl 4-(trans-4-n-decylcyclohexyl)benzoate (10XPCHB) have been studied. Compounds CBnAB are smectic A₁ for n ≤ 7 and smectic A_d for n ≥ 8; compounds 10XPCHB are smectic A, only. It was found that the S_Ad phase of compounds CBnAB exhibits ideal miscibility with the S_A1 phase of compounds 10XTCHB, and that the S_A1 phases of both compounds show abnormal behaviour. The S_A1 phase of compounds CBnAB is destabilized and the range of the S_A1 phase is enhanced on the side of 10XPCHB. The reasons for this behaviour are discussed.     

New 1,3-dithiane type ionic liquid crystal compounds

New pyridinium type thermotropic ionic liquid crystal materials having a 1,3-dithiane ring in their central core, N -substituted-4-(5-alkyl-1,3-dithian-2-yl)pyridinium bromides ( 8 ), were synthesized. These compounds exhibited a smectic A phase over a very wide temperature range including room temperature.     

Synthesis and characterization of novel fluorinated diphenyldiacetylenic liquid crystals

Five series of asymmetric diphenyldiacetylenes containing a single fluorine, two fluorines or a trifluoromethyl group at one end and an alkyl, alkyloxy or alkenyloxy group on the other end, were prepared and characterized. Most of the 4-alkylphenyl-4'-fluorophenyldiacetylenes, 4-alkyloxyphenyl-4'-fluorophenyldiacetylenes and 4-alkenyloxyphenyl-4'-fluorophenyldiacetylenes obtained exhibit an enantiotropic nematic phase and no smectic phase. However, most of the 4-alkyl-3', 4'-difluorodiphenyldiacetylenes, 4-alkenyloxy-3',4'-difluorodiphenyldiacetylenes and 4-alkyl-4'-trifluoromethyldiphenyldiacetylenes show no mesomorphic behaviour. The effects of alkyl, alkyloxy, alkenyloxy, fluoro, 3,4-difluoro and trifluoromethyl end groups on the mesomorphic behaviour of the diphenyldiacetylenes prepared are discussed.     

Conductive liquid crystalline compounds having a piperazine structure

New conductive thermotropic liquid crystalline materials having a piperazine ring in the central core: 1-[4-(9-decenyloxy)phenyl]-4-alkylpiperazines ( 6 ) were synthesized. The mesomorphic behaviours of these compounds and their conductivity in the liquid crystal phase were measured. The principal features of these compounds are to exhibit a smectic B phase around room temperature (for example 6 : Cr 50 SmB 81 I, °C) and to exhibit a large dark current (6d: 430 μA cm^-2, applied voltage 20 V, at 70°C) in the smectic B phase.     

Structure and photoconductive behaviour of a sanidic liquid crystal

A series of [1]benzothieno[3,2-b][1]benzothiophene-2,7-dicarboxylate derivatives consisting of a flat, conjugated aromatic moiety containing sulphur hetero-atoms and substituted by terminal chains - ethyl, decyl, Z-4-decenyl or 2-(2-butoxyethoxy)ethyl - has been synthesized. These materials exhibit a smectic liquid crystalline phase, the stability of which was found to be strongly dependent on the length and the nature of the terminal chains. In the mesophase, the molecular arrangement within the smectic layer is characterized by a local stacking of the rigid parts similar to that found in discotic columnar systems. Finally, clear photoconductive behaviour was found in mechanically aligned samples of these liquid crystals.     

Mesomorphic behaviour of praseodymium(III) alkanoates

In this paper, we describe the synthesis, characterization and thermal behaviour of praseodymium(III) alkanoates. The compounds have the stoichiometry [Pr(C_xH_2x+1COO)₃], where x = 5-19, and were characterized by elemental analysis and infrared spectroscopy. The thermal behaviour was investigated by hot-stage polarizing optical microscopy, DSC and high temperature X-ray diffraction. A highly viscous mesophase M and a smectic A phase were observed for the shorter chain compounds (x = 5-8), whereas only a smectic A phase was observed for the longer chain compounds of this type of metallomesogens. The chain length has a pronounced effect on the transition temperatures.     

Conductive liquid crystalline compounds having a piperazine structure

New conductive thermotropic liquid crystalline materials having a piperazine ring in the central core: 1-[4-(9-decenyloxy)phenyl]-4-alkylpiperazines (6) were synthesized. The mesomorphic behaviours of these compounds and their conductivity in the liquid crystal phase were measured. The principal features of these compounds are to exhibit a smectic B phase around room temperature (for example 6: Cr 50 SmB 81 I, °C) and to exhibit a large dark current (6d: 430 μA cm^?2, applied voltage 20 V, at 70°C) in the smectic B phase.     

New ionic liquid crystal compounds having a 1,3-dithiane or 1,3-dioxane ring

New pyridinium type thermotropic ionic liquid crystal materials having a 1,3-dithiane ring in the central core N-substituted 4-(5-alkyl-1,3-dithian-2-yl)pyridinium bromides and the corresponding 1,3-dioxanes were synthesized and their mesomorphic behaviours compared. The principal feature of these compounds is to exhibit a smectic A phase over a very wide temperature range including room temperature.