Synthesis and liquid crystalline properties of a series of cholesterol‐based dimesogenic compounds

The synthesis and mesomorphic properties of a series of novel dimesogenic compounds containing the cholesteryl ester unit and a phenyl benzoate group are reported. The two mesogenic units of these compounds are linked through dicarboxylic ester bonds, with alkylene spacer lengths of 2, 4, 6 and 8 methylene units. The chemical structures and liquid crystalline properties of this series of compounds were characterized by FTIR, ¹H NMR, hot stage‐coupled polarizing microscopy and DSC. The results show that this series of compounds are cholesteric liquid crystals over a wide range, both during heating and cooling, and they exhibit iridescent colours in the liquid crystalline state.     

Comparison of liquid crystalline properties of dimeric compounds of different skeletal shapes

Series of dimeric compounds of different skeletal shapes consisting of two triad aromatic ester type mesogenic moieties connected via polymethylene spacers were synthesized and their liquid crystalline properties compared. The two mesogenic units are connected in either Hor T-shape or in linear fashion. In general, it was found that mesophase temperature ranges for the T- and linear-shaped compounds are much wider than for the H-shaped compounds. Moreover, the former are enantiotropic thermotropic materials, whereas the latter tend to be monotropic unless the spacer length is fairly long, i.e. longer than decamethylene. Among the three series, the linearly linked twin compounds had the highest melting and isotropization temperatures. All of the linear and T-shaped dimeric compounds reported in this article form only nematic mesophases.     

Comparison of liquid crystalline properties of dimeric compounds of different skeletal shapes

Series of dimeric compounds of different skeletal shapes consisting of two triad aromatic ester type mesogenic moieties connected via polymethylene spacers were synthesized and their liquid crystalline properties compared. The two mesogenic units are connected in either Hor T-shape or in linear fashion. In general, it was found that mesophase temperature ranges for the T- and linear-shaped compounds are much wider than for the H-shaped compounds. Moreover, the former are enantiotropic thermotropic materials, whereas the latter tend to be monotropic unless the spacer length is fairly long, i.e. longer than decamethylene. Among the three series, the linearly linked twin compounds had the highest melting and isotropization temperatures. All of the linear and T-shaped dimeric compounds reported in this article form only nematic mesophases.     

Synthesis and characterization of non-symmetrical liquid crystals containing a cholesteryl ester moiety

In this paper,a series of chiral non-symmetrical liquid crystals(nBA-chol)consisting of a cholesteryl ester moiety as chiral entity and a biphenyl aromatic core with different terminal alkyl chain has been synthesized and investigated for their liquid crystalline properties.Effects of numbers of methylene units in the terminal alkyl chain on the phase transition temperatures and on the temperature-dependent pitch lengths of the chiral liquid crystals have been studied.The long terminal alkyl chain tends ...     

Studies on thermotropic liquid crystalline polymer. XI. Effect of amide group on thermotropic liquid crystalline polymer properties

A series of poly(azomethine)s containing amide, ether, or ester groups was prepared by the condensation of dialdehydes with various diamines. The thermotropic liquid crystalline properties were examined by DSC and microscopic observations. The effects of the number and position of amide groups, which are attached to the rigid segment, on the thermotropic liquid crystalline properties of the homo-and copoly(amide-azomethine-ether)s were also investigated in this study. The copolymerization took place by changing the amount of amide group to obtain copoly(amide-azomethine) ( P13 and P14 ) which exhibit thermotropic liquid crystalline properties. The poly(azomethine)s containing ether or ester groups also exhibited thermotropic liquid crystalline properties. © 1993 John Wiley & Sons, Inc.     

Synthesis and physical properties of laterally fluorinated liquid crystals containing 1,3,2-dioxaborinane and cyclohexyl units

Six series of laterally fluorinated liquid crystals containing 1,3,2-dioxaborinane and cyclohexyl units have been synthesized and characterized. Their mesomorphic properties were characterized by polarizing optical microscopy and differential scanning calorimetry. All these compounds are thermotropic liquid crystalline materials. All three-ring compounds (series A, B and C) and most four-ring compounds (series D, E and F) exhibit only a nematic phase, while some four-ring compounds with long terminal alkyl chains show nematic, smectic A and even smectic B phases. In addition, four compounds containing a 1,3-dioxane unit were prepared, and their mesomorphic properties compared with their 1,3,2-dioxaborinane analogues. The dielectric anisotropies of selected target compounds were determined; some showed a negative anisotropy. The relationships between the properties and chemical structures of these new compounds are discussed.     

Cholesterol-containing liquid crystal dimers with ether linkages between the spacer and mesogenic units

Three series of chiral liquid crystalline dimers were investigated, having a cholesteryl and a cyanobiphenylyl, butoxybiphenylyl or hexyloxybiphenylyl group connected to a variable alkyl spacer through ether linkages. Their properties were compared with those of the corresponding ester derivatives. The phase behaviour of compounds with ether and ester linkages is comparable, showing N* and SmA phases. The melting points of the compounds with ether linkages are in the same range as those of the ester compounds, but the liquid crystal transition temperatures are lower. The smectic layer spacings and smectic ordering properties are also similar. The cyanobiphenylyl compounds have an interdigitated SmA layer structure, which shows a small odd–even effect with spacer parity. The alkoxybiphenylyl compounds have a monolayer SmA phase for short spacers and an intercalated SmA phase for longer spacers. The selective reflection wavelengths of the chiral nematic phase of the ether compounds are lower than those of the corresponding ester compounds. The transition from N* to interdigitated or monolayer SmA is accompanied by a strong increase in the selective reflection wavelength, indicative of an intermediate TGB phase. This is absent for the transition from N* to intercalated SmA.     

Cholesterol-containing liquid crystal dimers with ether linkages between the spacer and mesogenic units

Three series of chiral liquid crystalline dimers were investigated, having a cholesteryl and a cyanobiphenylyl, butoxybiphenylyl or hexyloxybiphenylyl group connected to a variable alkyl spacer through ether linkages. Their properties were compared with those of the corresponding ester derivatives. The phase behaviour of compounds with ether and ester linkages is comparable, showing N* and SmA phases. The melting points of the compounds with ether linkages are in the same range as those of the ester compounds, but the liquid crystal transition temperatures are lower. The smectic layer spacings and smectic ordering properties are also similar. The cyanobiphenylyl compounds have an interdigitated SmA layer structure, which shows a small odd-even effect with spacer parity. The alkoxybiphenylyl compounds have a monolayer SmA phase for short spacers and an intercalated SmA phase for longer spacers. The selective reflection wavelengths of the chiral nematic phase of the ether compounds are lower than those of the corresponding ester compounds. The transition from N* to interdigitated or monolayer SmA is accompanied by a strong increase in the selective reflection wavelength, indicative of an intermediate TGB phase. This is absent for the transition from N* to intercalated SmA.     

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.     

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.     

分子中部含齐聚氧化乙烯单元的酯-醚液晶

以4-(4′-烷氧基苯甲酰氧基)苯甲酸作为液晶中间体,合成了在分子中部含齐聚氧化乙烯的系列酯-醚液晶化合物.对其化学结构和液晶性能进行了表征,除个别化合物外,其余样品均具有热致液晶性.     

Synthesis,characterization and thermal properties of 4,4'-bis(4-n-alkoxybenzoyloxy)benzylideneanilines and bis(4-benzylidene-4'-n-alkoxyaniline) terephthalates

Series of novel thermotropic liquid crystalline compounds which serve as models for mesogenic diols have been synthesized. The mesogen molecules are constructed from 1,4-disubstituted benzene rings linked through ester and azomethine units. Based on the number of phenyl rings, a tetrad or pentad classification has been assigned to the core molecule. The structures of these compounds were established by FTIR and NMR spectroscopy, while the mesomorphic behaviour has been confirmed using polarizing optical microscopy and DSC. All the compounds of the homologues series are mesomorphic in nature. The lower members of the series are nematogenic, while the higher members exhibit both nematic and smectic character, with high melting behaviour and wide mesophase ranges.     

Synthesis and physical properties of laterally fluorinated liquid crystals containing 1,3,2-dioxaborinane and cyclohexyl units

Six series of laterally fluorinated liquid crystals containing 1,3,2-dioxaborinane and cyclohexyl units have been synthesized and characterized. Their mesomorphic properties were characterized by polarizing optical microscopy and differential scanning calorimetry. All these compounds are thermotropic liquid crystalline materials. All three-ring compounds (series A, B and C) and most four-ring compounds (series D, E and F) exhibit only a nematic phase, while some four-ring compounds with long terminal alkyl chains show nematic, smectic A and even smectic B phases. In addition, four compounds containing a 1,3-dioxane unit were prepared, and their mesomorphic properties compared with their 1,3,2-dioxaborinane analogues. The dielectric anisotropies of selected target compounds were determined; some showed a negative anisotropy. The relationships between the properties and chemical structures of these new compounds are discussed.     

Synthesis and characterization of new series of ferroelectric liquid crystals containing oligooxyethylene spacers

Four series of ferroelectric liquid crystals containing oligooxyethylene spacers have been synthesized. These obtained liquid crystal compounds were characterized by NMR, differential scanning calorimetry (DSC) and optical polarized microscopy (POM). The properties of the liquid crystalline phase were investigated as a function of spacer units, numbers of core aromatic rings, and different terminal asymmetric moieties. It was found that (i) the phase transition temperature decreased with the increasing oligooxyethylene spacer unit, (ii) the liquid crystalline phases were enhanced in three phenyl ring system than in two phenyl ring system, and (iii) ferroelectric liquid crystals containing different terminal asymmetric moieties exhibited novel mesophase phenomena. A twist grain boundary phase (TGB_A phase) was observed in some compounds of this study. Furthermore, a wide temperature chiral smectic Crange including room temperature was achieved.     

Effect of alkyl chain length in the terminal ester group on mesomorphic properties of new chiral lactic acid derivatives

Two series of new liquid crystalline lactic acid derivatives with a terminal ester group have been synthesised. The effect of this ester unit and the length of its alkyl chain on the mesomorphic and dielectric properties of the compounds exhibiting a broad temperature range of chiral smectic phases have been studied. We found that the mesomorphic behaviour and phase transition temperatures are strongly affected by the molecular architecture. Depending on the alkyl chain length in the terminal ester unit, the studied materials exhibited paraelectric smectic A*, ferroelectric tilted smectic C* and antiferroelectric smectic C_A* phases over a broad temperature range. The physical properties of the compounds have been studied by optical polarising microscopy, differential scanning calorimetry, electro-optic measurements, small-angle X-ray scattering and dielectric spectroscopy. Furthermore, the homologues with short terminal alkyl chains showed a very small layer shrinkage at the transition from the orthogonal SmA* to the tilted SmC* phase, which is a characteristic feature of ‘de Vries-type’ behaviour.     

Non-symmetrically (1,2,4- and 1,3,4-)oxadiazole homologous: synthesis,characterisation and study the effect of different substituents on their mesophase behaviours

We have previously demonstrated that the type of oxadiazole isomers is relatively affected on showing the liquid crystalline properties of the compounds that have the same chemical compositions. In this paper, we presented the synthesis and mesomorphic behaviour of related compounds that possess ester linkage with different substituted groups on para of the phenyl to six derivatives containing 1,3,4-oxadiazole and like another six containing 1,2,4-oxadiazole rings. The formation of these compounds was evidenced by FTIR, ¹H NMR, ¹³C NMR, elemental analysis and mass techniques. Their mesophase behaviours were studied by optical polarised microscopy (OPM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). All of them presented liquid crystalline properties with nematic (N), smectic A (SmA) and smectic C (SmC) phases typically to calamitic compounds. The effect of substituent group nature and the type of oxadiazole isomers on the liquid crystalline properties of these compounds are analysed and discussed.     

Synthesis and liquid crystalline properties of T-shaped dimesogenic compounds

Two series of new dimesogenic liquid crystalline compounds were synthesized and their LC and other thermal properties were characterized. These compounds consist of two mesogenic units connected through polymethylene spacer of varying length in the shape of the letter ‘T’. The difference between the two series is in the structure of tail groups attached on the pendant azobenzene mesogens; one of which is n-butyl and the other is phenyl. The compounds were characterized for their liquid crystallinity by the differential scanning calorimetry (DSC), X-ray diffractometry and visual observation of the melts on a hot-stage attached to a polarizing microscope. All these compounds were found to form only the nematic phase enantiotropically.     

New Schiff's bases containing 1,3,4-thiadiazole and 1,3,4-oxadiazole units: a study of the effect of the heterocyclic ring and the position of the lateral alkoxy group on liquid crystalline properties

The synthesis of novel Schiff's bases incorporating the five-membered 1,3,4-thiadiazole (series 7, 9) and 1,3,4-oxadiazole (series 8, 10) rings have been prepared and their liquid crystalline properties studied. All compounds of series 7 exhibit an enantiotropic smectic C phase. No liquid crystalline properties were observed for the compounds of series 8-10. A study of the structure/mesomorphic activity relationship is also described.     

New Schiff's bases containing 1,3,4-thiadiazole and 1,3,4-oxadiazole units: a study of the effect of the heterocyclic ring and the position of the lateral alkoxy group on liquid crystalline properties

The synthesis of novel Schiff's bases incorporating the five-membered 1,3,4-thiadiazole (series 7, 9) and 1,3,4-oxadiazole (series 8, 10) rings have been prepared and their liquid crystalline properties studied. All compounds of series 7 exhibit an enantiotropic smectic C phase. No liquid crystalline properties were observed for the compounds of series 8-10. A study of the structure/mesomorphic activity relationship is also described.     

4-Octylphenylazo-4′-phenyl alkanoates – homologous series of azomesogens with extremely rich liquid-crystalline polymorphism

This paper presents synthesis and liquid-crystalline properties of full homologues series (from acetate to arachidate) of 4-octylphenylazo-4′-phenyl alkanoates. All of the 19 synthesised compounds are liquid crystals with extremely rich mesomorphism. The ester chain length strongly influences mesogenic behaviour of presented materials. In some compounds, up to four liquid-crystalline phases have been observed. There were six different mesophases detected: nematic, smectic C, smectic F, smectic I, J and G. Moreover, some homologues display two crystalline forms. This latter phenomenon does not depend on the ester chain length. Identification of such complicated phase sequences was made based on four methods: polarised light microscopy, thermo-optical analysis, differential scanning calorimetry and X-ray measurements.