Fluorescent liquid crystalline compounds with 1,3,4-oxadiazole and benzo[b]thiophene units

A series of fluorescent liquid crystalline compounds containing 1,3,4-oxadiazole and benzo[b]thiophene units have been prepared. In CH₂Cl₂ solution, these compounds displayed a fluorescent emission with λ_max at 422–426 nm and quantum yields of 41–48%. Most of them exhibited thermotropic liquid crystalline properties with nematic and/or smectic A phases with excellent thermal stability. This work revealed that longer terminal alkoxy chains would be detrimental to the formation of mesophases for such kind of compounds. The effect of the terminal groups on mesomorphic and spectroscopic property is discussed.     

T-shaped non-symmetrical twin liquid crystalline compounds

New unconventional T-shaped non-symmetrical dimeric liquid crystalline compounds have been synthesised and their thermotropic properties studied on the hot-stage of a polarising microscope. These compounds consist of an azo-ester mesogenic unit with a range of terminal substituents (–CH₃, –OCH₃, –NO₂ or –Cl) at one end, interconnected by a flexible spacer (n?=?4, 5 or 10) via ether and ester linking units to a biphenyl moiety at the lateral hydroxyl position of the azo-ester. All the compounds were characterised using a combination of elemental analysis and standard spectroscopic methods. The compounds were found to exhibit enantiotropic nematic and smectic mesophases. The effect of different terminal substituents on mesomorphism is discussed.     

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.     

Preparation and properties of lateral monofluoro-substituted benzoxazole-based mesogenic compounds

A series of 2-(3?-fluoro-4?-alkoxy-1,1?-biphenyl-4-yl)-benzoxazole liquid crystals (coded as nPF(3)PBx) were prepared, where a lateral fluorine substituent, as well as methyl, chlorine and nitro terminal groups, was introduced into the molecules to investigate the effects of different polar substituents on the liquid crystal properties. The mesomorphic and photophysical properties were investigated. The results show that compounds nPF(3)PBx have enantiotropic mesophases; meanwhile, they exhibit UV–vis absorption bands with maxima at 323–326 nm and photoluminescence emission peaks at 389–395 nm, respectively. It is noted that nPF(3)PBx with terminal polar groups or electron-withdrawing groups (NO₂, Cl) display higher clearing temperatures and wider mesophase range than those of the corresponding homologues with terminal non-polar groups or electron-donating groups (CH₃, H). Meanwhile, compared with two lateral fluorine-substituted analogues containing 3,5-difluorophenyl unit, lateral monofluoro-substituted nPF(3)PBx display enhanced mesophase range both in heating and cooling except for terminal methyl-substituted compounds, as well as show obvious red-shifted UV–vis absorption bands and photoluminescence emission, which are attributed to the enhanced dipole–dipole interaction caused by increased dipole moment.     

Effect of terminal aryl rings of liquid crystal trimers on liquid crystalline properties

Liquid crystalline properties of five series of biphenyl derivatives connected with p-nitrophenyl, phenyl, 2-naphthyl, 9-phenathryl and bromo as the terminal groups via flexible spacers were studied. All the compounds exhibited nematic phase. The nematic–isotropic or isotropic–nematic transition properties resulted in an odd–even effect as the length of the spacers was varied, in which the even members exhibited higher values, for the compounds with p-nitrophenyl, phenyl, 2-naphthyl and 9-phenanthryl groups, while the transitional properties of the compounds substituted with bromo atom as the terminal group instead of the aryl groups did not show such odd–even effect. These results suggest that the aryl rings, such as p-nitrophenyl, phenyl, 2-naphthyl and 9-phenanthryl groups, play a role of mesogen while the terminal bromo atom does not. The effect of the terminal aryl rings on the liquid crystalline properties will be reported.     

Symmetrical and asymmetrical liquid crystal dimers: synthesis,characterisation and mesomorphic behaviour

ABSTRACT

A series of new asymmetrical liquid crystal dimers, R_nO–S2O–OR_n (n = 2–10), linked by an ethylene spacer having carbothiol – COS – and carboxyl – COO – linkages to the core centre of the molecule and bearing different lengths of terminal alkoxy chains were synthesised in order to study the effects of the length of the terminal alkoxy chains on mesomorphic properties. As well as, five symmetrical and asymmetrical dimers linked by butylene spacers bearing different linkages to the core and various terminal chains were also synthesized in order to study the effect of the nature of the spacer and terminal groups. The structures of the synthesised dimers were confirmed by physico-chemical techniques, i.e. FTIR, NMR and mass spectra. Differential scanning calorimetry and polarising optical microscopy verified the liquid crystal behaviour transition temperatures. The isotropic transition temperatures of the dimers R_nO–S2O–OR_n (n = 2–10) decreased with increasing length of alkoxy chain. Structural effects on the mesomorphic and physical properties were investigated in terms of alteration of carboxylate and thioester groups linking the spacer. The mesomorphic investigation reveals that all the dimers formed an enantiotropic Nematic phase except for dimer HO2SH which is not a liquid crystal.     

Cholesterol-based dimeric liquid crystals: synthesis and mesomorphic behaviour

Chiral non-symmetric dimeric liquid crystals consisting of a cholesteryl ester moiety as chiral entity and a biphenyl aromatic core, interconnected through n-butyl (C₄) or n-pentyl (C₅) parity alkylene spacers, have been synthesized and investigated for their liquid crystalline properties. All the dimers exhibit enantiotropic mesophases. The first member of the dimers having the C₄ central spacer exhibit only the chiral nematic (N*) mesophase, while the higher homologues also show smectic A (SmA) and twist grain boundary (TGB) mesophases. The dimers of the other series containing the C₅ central spacer also have stable SmA, TGB and N* mesophases, except for the first which does not show the TGB phase. Both series of compounds show a weak odd-even effect with terminal alkyl chain substitution, while the spacer length has a marked influence on the phase transition temperatures.     

Effect of hydrogen-bonded supramolecular assembling on liquid crystal properties of imidazole-containing azomethines and their chelates with copper(II)

A series of imidazole-containing rod-like Schiff's bases and their ionic copper(II) chelates with various lengths of the terminal alkyl chain containing 6, 8, 10, 12, 14 and 16 carbon atoms have been synthesised. The synthesised compounds were characterised by elemental analyses, ¹H NMR, IR and UV–vis and mass spectroscopies. Thermotropic smectic C mesophases in the ligands and smectic A mesophases in the copper(II) complexes were identified using POM, DSC and small-angle XRD scattering methods. X-ray diffraction patterns of the prepared imidazole imines indicate to supramolecular self-assembled structures in the liquid crystal state, which are formed by means of intermolecular hydrogen bonds. It was established that both liquid crystal arrangement and supramolecular assemblies in ligands disappeared near 190°C, mainly regardless of the lengths of the terminal alkyl chains. Contrary, assembling of the copper(II) complexes into supramolecular bilayers occurs near 200°C, which causes their transition to a smectic A mesophase.     

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 ...     

Synthesis and mesomorphic properties and optical behaviour analysis of homologous series azobenzene liquid crystal monomer with polar substituents

ABSTRACT

Twenty novel azobenzene liquid crystal micromolecular compounds named ω-[4-(p-substituted azobenzeneoxy carbonyl]acid (X-ABCnA) have been designed and synthesised, followed by studies on the thermal performance and mesomorphic properties of the compounds. The liquid crystal compounds were divided into five homologous series based on the terminal substituents R (R = CH₃O, CH₃, H, Cl, NO₂). In each series, the number of carbons on flexible chain was 4, 6, 8 and 10, respectively. Fourier-transform infrared, proton nuclear magnetic resonance and elementary analysis demonstrated that the structure of the synthesised azobenzene liquid crystal compounds was consistent with the molecular design. The mesomorphic properties were tested, analysed and characterised by using differential scanning calorimetry and polarised optical microscopy. The melting transition (T _m) of all the compounds in homologous series with different substituents appeared to decrease with the increase of carbon numbers on flexible chains. The same held true for the temperature of isotropic-mesophase/crystalline transition. The compounds with stronger polarity of terminal substituents were more likely to form broader mesogenic ranges. The liquid crystal compounds discussed in this work can be regarded as a reference for the synthesis of mesogenic arms participating in the synthesis of novel multi-arm liquid crystalline macromolecules and polymers.     

Synthesis and mesomorphic properties of chiral liquid crystal dimers derived from azobenzene and substituted naphthol

Symmetrical liquid crystal dimers bis{2-alkyl-(S)-(+)-2-(6-[4-4′-decyloxyphenylazo)-benzoyloxy]-2-naphthyl)propinate} have conveniently been designed, synthesised and their mesomorphic properties were investigated. These dimers possess two identical mesogenic units with each of them attached to the terminal end of a flexible spacer (–C _n H_2n ; where n = 6–10). The respective mesogenic unit was made up from a naphthyl ring attached to the alkyloxylated azobenzene via the ester (COO–) bond. The chiral moiety attached to the 6-position of the naphthyl ring possesses a terminal carboxylic group COO– which linked up the mesogenic unit and the spacer. The thermal and optical properties for the ultimate compounds at different temperature were studied explicitly with the aids of differential scanning calorimetry and polarising optical microscopy. All dimers exhibit unambiguously the monotropic nematic and smectic A phases. The homeotropic alignment of the molecules within the anisotropic region was further confirmed through the application of homogeneously treated cell.     

Fabrication of vertical alignment liquid crystal cell without forming a conventional polyimide-alignment layer

Two series of asymmetric banana-shaped compounds have been synthesized and studied. In the 1,3-phenylene bis[4-(4′-alkoxybenzoyloxy)]benzoate series the lack of symmetry was derived solely from the difference in length of the two terminal alkoxy chains. In the 3,4′-biphenylene bis[4-(4′-alkoxybenzoyloxy)]benzoate series the asymmetric nature originates from the 3,4′-substitution of the central biphenyl group and from the difference in length of the two terminal chains. All the melting points of the asymmetrical compounds in the series with the central phenyl unit are lower than those of the symmetrical compounds. The liquid crystalline B₁ or B₂ phase was retained in all cases. In the series with the central biphenyl unit the compounds with the shortest chain attached to the para-position of the central biphenyl unit have the lowest melting points. A significant lowering of the melting points in comparison with the symmetrically substituted compounds, however, could not be achieved. All the compounds of both series show a layer spacing which is comparable to those of the symmetrically substituted parent compounds. The observed switching behaviour of both the symmetric and asymmetric compounds with a B₂ phase was antiferroelectric.     

Polymerizable liquid crystalline twin molecules: synthesis and thermotropic properties

The synthesis of 14 novel low molar mass liquid crystalline twin molecules is described and experimental details are given. The twin monomers contain two mesogenic units which are connected by a flexible spacer. Two terminal acrylate groups make these twins suitable for photopolymerization. The insertion of lateral groups into the mesogen leads to glassforming properties. We tested several substituents (-OCH₃, -CH₃) in different positions of the mesogenic unit and investigated their thermotropic properties as well as their crystallization behaviour by polarizing microscopy and DSC experiments. Some of the novel twin molecules with lateral substituents in the mesogenic core have unusually broad mesophases of about 150^oC. Below T _g stable LC glasses are formed. At room temperature a slow, kinetically hindered crystallization starts after about three hours. The broad mesophases of the twin molecules allow investigations of the photopolymerization kinetics over a wide temperature range. The addition of chiral non-liquid crystalline comonomers and subsequent photopolymerization leads to cholesteric networks with interesting optical properties. Last but not least, the twins are suitable mixing agents which suppress the crystallization of classical mono-rods.     

Cholesterol-based dimeric liquid crystals: synthesis and mesomorphic behaviour

Chiral non-symmetric dimeric liquid crystals consisting of a cholesteryl ester moiety as chiral entity and a biphenyl aromatic core, interconnected through n-butyl (C₄) or n-pentyl (C₅) parity alkylene spacers, have been synthesized and investigated for their liquid crystalline properties. All the dimers exhibit enantiotropic mesophases. The first member of the dimers having the C₄ central spacer exhibit only the chiral nematic (N*) mesophase, while the higher homologues also show smectic A (SmA) and twist grain boundary (TGB) mesophases. The dimers of the other series containing the C₅ central spacer also have stable SmA, TGB and N* mesophases, except for the first which does not show the TGB phase. Both series of compounds show a weak odd-even effect with terminal alkyl chain substitution, while the spacer length has a marked influence on the phase transition temperatures.     

Oxadiazole-based unsymmetrical chiral liquid crystal dimers: synthesis and mesomorphic properties

The synthesis and liquid crystalline properties of novel chiral Schiff's base dimers containing the 1,3,4-oxadiazole ring are reported. The length of the terminal S-alkyl chain has been varied. All the compounds synthesised were thermally stable and exhibited enantiotropic mesomorphism, showing either SmC*–SmA–TGB–N*–BP or SmC*–SmA phase sequence.     

Antiferroelectric and ferrielectric liquid crystalline low molar mass materials and polymers

Novel liquid crystalline Low Molecular Mass (LMM) materials bearing two chiral lactate groups, as well as compounds of like structure to MHPOBC have been synthesized. All the LMM compounds exhibit the SmC*A (antiferroelectric) and/or SmC*gamma (ferrielectric) phases. The mesogens have been incorporated as pendant groups on polymer backbones of three different natures to prepare side chain liquid crystalline copolysiloxanes, homopolysiloxanes and homopolyacrylates. The investigation of the polymers by means of miscibility studies showed that the antiferro- and ferri-electric phases are strongly destabilized in the coposiloxanes and homopolysiloxanes, while in the homopolyacrylates a large temperature range mesophase is found to be miscible with the SmC*A phase. The physical properties of the mesophases and their stability, both for the LMM materials and the polymers, are presented and discussed.     

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 characterization of luminescent hockey stick‐shaped liquid crystalline compounds

A general synthetic strategy, based on a convergent approach, allowed us to prepare a series of luminescent unsymmetrical bent‐core compounds (2,5‐(disubstituted)‐1,3,4‐oxadiazole derivatives), via the Sonogashira crosscoupling reaction, all possessing a similar hockey stick shape. Their mesophases were characterized using polarizing optical microscopy and differential scanning calorimetry. The observed LC phases possess the classical textures of calamitic liquid crystals. Fluorescence in solution for these compounds exhibits strong blue emission (λ_{max em.} = 390–460 nm) with good quantum yields (50–85%).     

Electro-optical investigations and effect of asymmetry in bent-core liquid crystals

We report the synthesis and mesomorphic properties of a homologous series (10a–10g) of bent-core molecules constructed through covalent linkage of structurally non-symmetrical rod-like mesogens connected with a 1, 3-phenylene unit. The study of homologous series underlines the importance of length and nature of terminal chains. The homologues of shorter chains show a typical non-switchable rectangular columnar B₁ phase, while the switchable lamellar (B₂) phase is induced on moving to higher homologues. X-ray diffraction patterns indicate the presence of B₁ and B₂ mesophases. Polarised optical microscopy investigations under electric field in the B₂ phases revealed the existence of anticlinic antiferroelectric texture. The measured spontaneous polarisation value in one of the compounds is 936 nC cm^?2, a high polarisation value in bent-core liquid crystals.