Synthesis and mesomorphic properties of fluoro and isothiocyanato biphenyl tolane liquid crystals

Four series of high birefringence biphenyl tolane liquid crystals having a terminal isothiocyanato or fluoro group were synthesized; their mesomorphic properties were studied by optical polarizing microscopy and DSC. These biphenyl tolane compounds exhibit reasonably low melting points and high birefringence of 0.37-0.49. By using these compounds a eutectic mixture was formulated exhibiting a wide nematic range, high figure-of-merit and low viscosity.     

Synthesis and mesomorphic properties of four-ring liquid crystals containing cyclohexyl,phenyl and pyridyl units

Two series of chiral and achiral 4-[(3-n-alkoxycarbonylpyridyl)-6-ethynyl]phenyl 4-(trans-4-n-alkylcyclohexyl)benzoate liquid crystals have been synthesized. Their mesomorphic properties were observed and measured by polarizing optical microscopy and DSC. A broad chiral smectic C phase was observed when terminal chains contained a chiral centre.     

Synthesis and mesomorphic properties of chiral fluorinated liquid crystals

Some fluorinated chiral liquid crystals were synthesized and the compounds characterized by IR, ¹H NMR, ¹⁹F NMR and mass spectroscopy and elemental analysis. Their phase transition behaviour was investigated by differential scanning calorimetry and polarizing optical microscopy. Nearly all of the compounds synthesized are liquid crystals with an enantiotropic cholesteric phase. Some of them exhibit a blue phase. Lateral tetrafluoro substitution decreases the clearing point and molecular polarity affects the formation of liquid crystalline phases.     

Synthesis and mesomorphic properties of four-ring fluorinated liquid crystals with trifluoromethyl group

The discovery of nematic phase in 3-fluoro-4-trifluoromethyl-4?-(4?-alkyl [trans, trans-1,1?-bicyclohexyl]-4-yl) 1,1?-biphenyls (n = 2, 3, 4, 5) is an accidental affair. A convenient method was used for the synthesis of these target compounds. After the preparation of the intermediate with trifluomethyl group, the target compounds were synthesised by Suzuki cross-coupling reaction. Then, these phase transition temperatures were measured by polarising textural observation, which confirmed the existence of single nematic phase. These temperatures were also measured by differential scanning calorimetry, which showed that the clearing point of compound (n = 3) is 267℃. The possible mechanism of occurrence of unique nematic phase was discussed on the basis of the principles of fluorine chemistry.     

Synthesis and properties of allyloxy-based tolane liquid crystals with high negative dielectric anisotropy

A series of tolane liquid crystals (LCs) containing 2,3-difluorophenyl and allyloxy terminal groups have been synthesised via multi-step reactions. Their thermotropic mesophases, birefringences and dielectric anisotropy properties are discussed by comparison with the non-fluorinated analog. The results show that the allyloxy-based tolane LC 3TOV reveals a high value of the birefringence (0.29), negative dielectric anisotropy (?4.44) and a broad nematic mesophase with a low melting point and high clearing point. The effects of the terminal alkyl chains, the lateral fluoro substituents, the allyloxy terminal group and alkyne bridge on the mesomorphic and physical properties were also discussed. Meanwhile, Density Functional Theory (DFT) calculations of molecular conformation and polarisability were used to correlate the experimental findings.     

Synthesis and mesomorphic properties of novel fishbone-like liquid crystalline polysilsesquioxanes VI. Fishbone-like,ester-based liquid crystalline polysilsesquioxanes

Two novel kinds of fishbone-like, ester-based, liquid crystalline, random copolysilsesquioxanes, LC₁-CH₃-P and LC₂-CH₃-P, have been synthesized for the first time by stepwise coupling polymerization (SCP) from trichlorosilane monomers (RSiCl₃) containing mesogenic ester groups, using three main steps including preaminolysis, hydrolysis and polycondensation. Two new monomers 4-(11-trichlorosilylundecloyloxy)phenyl 4-methoxybenzoate (M₁) and 4-(3-trichlorosilylpropoxy)phenyl 4-methoxybenzoate (M₂) have been synthesized by hydrosilylation reaction of trichlorosilane and the mesogens 4-n-undecenoyloxyphenyl 4-methoxybenzoate and 4-allyloxyphenyl 4-methoxy-benzoate, respectively, in the presence of dicyclopentadienylplatinum(II) chloride (Cp₂Ptcl₂) catalyst. The structures and mesomorphic properties of LC₁-CH₃-P and LC₂-CH₃-P were investigated by FTIR, ¹H NMR, ¹³C NMR, ²⁹Si NMR, gel permeation chromatography, polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. It is proposed from the characterization data that these two polymers not only have an ordered ladder-like, double main chain, but also show thermotropic smectic behaviour with high clearing points and wide mesophase ranges (ΔT), which may hold promise for potential applications as highly stable gas chromatographic stationary phases.     

Synthesis and mesomorphic properties of super high birefringence isothiocyanato bistolane liquid crystals

Four series of high birefringence bistolane liquid crystals containing isothiocyanato termal groups were synthesized and characterized. As well as the phenyl group, both biphenyl and naphthyl moieties were introduced to enhance the birefringence. These bistolane compounds exhibit reasonably low melting points and high birefringence of 0.5-0.8. A eutectic mixture was formulated from these compounds exhibiting a wide nematic range, high figure-of-merit and low viscosity.     

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.     

Synthesis and mesomorphic properties of novel tolane-type liquid crystals

Two series of novel tolane-type liquid crystals(LCs) comprising of hydrogen-bonded organic acids were synthesized.The formation of dimerized H-bond LCs was confirmed by IR spectroscopy,and mesomorphic properties of the LCs were investigated by differential scanning calorimetry(DSC) and polarizing optical microscopy(POM).It was found that the end groups of the liquid crystals as well as the unsaturated rigid core had effect on the mesomorphic properties.     

Heterocyclic pyridine-based liquid crystals: synthesis and mesomorphic properties

A series of new calamitic liquid crystals, 4-{[(pyridin-4-yl)methylidene]amino}phenyl 4-alkoxybenzoates comprising a heterocyclic (pyridine) and two phenyl rings core system, terminal alkoxy chain, imine and ester linkers were synthesised and characterised. This series consists of nine members wherein the members differ by the length of alkoxy chain (C_nH_2n+1O–, where n = 2, 4, 6, 8, 10, 12, 14, 16, 18). Spectral analysis results were in accordance with the expected structure. Their thermotropic behaviours were studied by using differential scanning calorimetry, optical polarising microscopy and powder X-ray diffraction techniques. A single mesophase (nematic) was observed for the first three members of the series (n = 2, 4 and 6). As the alkoxy chain increased to n = 8 and n = 10, the nematic phase appeared together with an additional smectic A (SmA) phase. When moving from n = 12 until the highest members (n = 18), the nematic phase disappeared and these compounds only exhibited a single mesophase (SmA).     

Synthesis and mesomorphic properties of three- and four-ring liquid crystals containing cyclohexyl,phenyl and pyridyl units

Two series of 4-(3-alkoxycarbonylpyridyl-6-ethynyl)phenyl trans-4-n-alkylcyclohexylcarboxylates and 4-(3-alkoxycarbonylpyridyl-6-ethynyl)phenyl 4-(trans-4-n-alkylcyclohexyl)benzoates have been prepared. Their mesmorphic properties were observed and measured by polarizing optical microscopy and differential scanning calorimetry. The relationship between structures and properties is discussed, showing that the ferroelectric phase can be observed when chiral terminal chains exist.     

Synthesis and mesomorphic properties of three-benzene-ring-containing banana-shaped liquid crystals

A homologous series of three-benzene-ring-containing banana-shaped compounds, N,N-bis(4-alkylcarbonyloxybenzylidene)benzene-1,3-diamine, were synthesised by esterifying aliphatic acids with the three-benzene-ring bent core 1,3-phenylene-bis(4-hydroxybenzylideneamine). As the number of carbon atoms in the aliphatic acids increased from 1 to 12, 12 novel banana-shaped compounds resulted with increasing lengths in their terminal tails. The mesomorphic properties of this homologous series of three-benzene-ring-containing banana-shaped compounds were characterised by means of polarised optical microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical studies. Our results have demonstrated that this series of banana-shaped compounds can form mesophases, although each of their bent cores contains only three benzene rings.     

Synthesis and characterisation of some new chalcone liquid crystals

A series of new chalcones with four aromatic rings is synthesised and characterised. The chemical structures of chalcones are evaluated by Fourier transform-infrared spectroscopy, elemental analysis, ¹H and ¹³C nuclear magnetic resonance spectroscopic techniques. The compounds were investigated for liquid crystalline properties using differential scanning calorimetry and polarising optical microscopy with hot stage. The results indicate that the formation of mesophase type is dependent on the alkyl chain length at one end of the molecule. Compounds 9a–d with relatively shorter chains show SmA and nematic mesophases, whereas 9e–g exhibit SmC and SmA mesophases. Compound 9h having a cyano group at one end, exhibit SmA and nematic mesophases.     

Synthesis and mesomorphic properties of chiral nematic liquid crystals based on cholesterol

A new series of mesogenic compounds having a cholesteryl moiety has been synthesised by condensing p-amino benzoate of cholesterol and methoxy substituted 4-n-alkoxy cinnamoyl chlorides and their liquid crystalline properties has been studied. All the members of the series are enantiotropic and exhibit chiral nematic (N*) mesophase. The plot of transition temperatures versus number of carbon atoms in the alkoxy chain exhibits odd–even effect and falling tendency for N*–isotropic transition temperatures. The compounds exhibit oily streak textures that on slight disturbance change to the plane textures and show iridescent colours. High anisotropy, linearity and intermolecular hydrogen bonding confer rich mesomorphic properties on the system. Intermolecular hydrogen bonding arising from amide linkage can lead to supramolecular motifs.     

Sulfur makes the difference: synthesis and mesomorphic properties of novel thioether-functionalized imidazolium ionic liquid crystals

Novel thioether-linked imidazolium ionic liquid crystals were synthesized starting from methyl 2-mercaptoacetate. The mesomorphic properties were determined by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction. All mesogens displayed smectic A mesophase geometries with strongly interdigitated bilayer structures. Comparison of the thioether-linked imidazolium salts with the corresponding amine- and amide-linked imidazolium salts as well as simple N-alkyl-imidazolium salts showed that both mesophase width and stability increased with increasing softness of the linking unit, thus indicating the beneficial effect of sulfur. Additionally, an increase of the length of the linking unit decreased the interdigitation of the alkyl chains.     

The effect of terminal epoxy modification on the mesomorphic and thermal stability of biphenyl ester liquid crystals

ABSTRACT

A series of biphenyl ester compounds with alkenyl, alkyl, oxirane, and 1,3-dioxolane as the terminal groups have been synthesised for investigating the mesomorphic and thermal stability. Based on the same carbon skeleton, the allyl-terminated compound V1OLC has no mesophase, while the oxirane-terminated compound POLC not only has wider multiple smectic mesophase compared with the propyl-terminated compound 3OLC but also exhibits the best thermal stability. However, when the terminal groups change from oxirane to 1,3-dioxolane, EOLC shows neither mesophase nor the good thermal stability. In addition, with the extension of the terminal chains, the butyl-terminated compound 4OLC gives the widest smectic mesophase. These imply that the mesomorphic and thermal stability of these biphenyl ester compounds are dependent on the suitable terminal chain lengths and epoxy sizes. Meanwhile, Density Functional Theory (DFT) calculations were conducted to assist in analysing the experimental results.     

Synthesis and mesomorphic properties of resorcyl di[4-(4-alkoxy-2,3-diflorophenyl)ethynyl] benzoate liquid crystals

Two resorcyl di[4-(4-alkoxy-2,3-difluorophenyl)ethynyl] benzoate liquid crystals (A10 and A12) were prepared and their mesomorphic properties were observed. A large polarisation value was obtained with longer terminal chains.     

Enhancement of the nematic order of polar liquid crystals in thin cells

Experimental observations show that the nematic order parameter (S) is significantly enhanced as the thickness of the cell is reduced. However, calculations based on earlier theories are not in good agreement with the experimental data. We earlier developed a molecular mean field model that assumes that the medium with polar molecules consists of inter-converting anti-parallel and parallel pairs, to explain the molecular origin of the ‘two lengths’ model. The model has been used to explain effects such as double re-entrance and the effect of electric field on the nematic–isotropic transition temperature, T _NI. We have recently extended the Maier–Saupe (M–S) theory using an empirical variation of surface potential, to account for the enhancement in which a molecule near the surface is assumed to feel the mean field potential (M–S type) and also the surface-induced potential. Variation in the density of the medium due to variation of S has been ignored. In the present paper, the change in the relative proportion of the parallel pairs due to changes in the density of the medium is included in the M–S theory with the surface potential. This results in improved agreement with the experimental data.     

Synthesis and characterisation of imidazolium-based ionic liquid crystals bearing a cholesteryl mesogenic group

A series of cholesteryl-containing imidazolium chlorides and imidazolium tetrachloroaluminates were synthesised, and the chemical structure, liquid crystalline behaviour and ionic conductivity were characterised by several technical methods. Whereas the imidazolium chlorides show chiral smectic A (SmA*) phase on heating and cooling cycles, the imidazolium tetrachloroaluminates display chiral nematic (N*) phase, which is uncommon for ionic liquid crystals (ILCs). The imidazolium chlorides display similar phase transition temperature and entropy, indicating the cholesteryl component influence predominately on the phase transition rather than the different alkyl substituent groups. The imidazolium tetrachloroaluminates show lower melting point temperatures and lower clear point temperature than the imidazolium chlorides. The mesophases exist at rather moderate temperatures. Non-mesomorphic imidazolium tetrachloroaluminate(III) salts with short alkyl substituents have been known for a long time, and the synthesised imidazolium tetrachloroaluminates are the first examples of tetrahalogenoaluminate(III)-containing ILCs. For the imidazolium tetrachloroaluminates, imidazolium cations combine loosely with AlCl₄^? ions because AlCl₄^? ions are large and occupy more space in spite of the hydrogen bond and electrostatic attraction interaction, indicating that the layer structure can be destroyed easily to form N* phase on heating.     

Synthesis and liquid crystalline behavior of azulene-based liquid crystals with 6-hexadecyl substituents on each azulene ring

Hexakis(6-hexadecyl-2-azulenyl)benzene (1b) has been synthesized by Co₂(CO)₈-catalyzed cyclotrimerization reaction of bis(6-hexadecyl-2-azulenyl)acetylene (2b). The mesomorphic behaviors of 1b, 2b, and 6-hexadecyl-2-phenylazulene (3b) were studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction (XRD) techniques and their mesomorphic properties were compared with those of their 6-octyl derivatives 1a, 2a, and 3a. Increase of the number of carbon atoms in the peripheral side chains drops the isotropization temperatures of 1b, 2b, and 3b by 56.9 °C, 33 °C, and 23.6 °C, respectively. Additionally, the phase-transition behavior varied with increase of the number of the peripheral chains, as well as decrease of the crystalline-mesophase transition temperatures, except for compound 3b. As the results, spontaneous monodomain homeotropic molecular alignment was revealed by compound 1b in its Col_hd mesophase on non-treated glass substrate, which would be attracted to the application for the device fabrication of molecular materials.