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.     

Liquid crystalline compounds with V-shaped molecular structures: synthesis and characterization of new azo compounds

The synthesis and mesomorphic properties of a series of 1,2-phenylene bis[4-(4-alkyloxyphenylazo)benzoates] are reported. The mesophases exhibited by these bent-shaped azo compounds are identified as nematic, smectic A and crystal E phases. All these compounds have fairly low transition temperatures, and so are suitable for physical studies. It has been concluded that the -CH N- linkage can be more conducive to mesomorphism compared with the -N N- linkage.     

Hockey stick-shaped azo compounds: effect of linkage groups and their direction of linking on mesomorphic properties

Several new hockey stick-shaped azo compounds are designed and synthesised with an aim to study the effect of different types of linkages and their direction of linking on the mesomorphic properties in such systems. The new compounds synthesised are characterised by spectroscopic methods. The liquid crystalline properties are investigated using polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) studies. They exhibited a variety of mesophases such as nematic (N), smectic A (SmA), anticlinic smectic C (SmC_a), B₁, etc. We found that the direction of linkage groups has a major effect on the mesomorphic properties when compared to the effect of different types of linkage groups. We observed a reversible photo-switching phenomenon of these compounds in their solution UV–vis spectra.     

λ-Shaped azomesogens with polar chloro- and nitro-substituents

A new homologous series of λ-shaped mesogenic azo esters with polar chloro- and nitro- substituents has been synthesised by attaching a rigid 2-chloro-4-nitrophenylazo group to a resorcinol moiety by a central azo linkage. Both phenolic hydroxyl groups are esterified by 4-n-alkoxybenzoyl groups. All the compounds synthesised have been characterised using a combination of elemental analysis and standard spectroscopic methods. The mesomorphic properties of the compounds have been determined by polarising optical microscopy and differential scanning calorimetry. The lower members of the series are non-mesogenic, the middle members exhibit a nematic mesophase, and higher members exhibit a smectic A mesophase. The effect of polar chloro-, nitro-, and long lateral aromatic substituents, on mesomorphism is discussed.     

Azo-functionalised achiral bent-core liquid crystalline materials: effect of presence of –N=N– linkage at different locations in the molecular architecture

Here, we report four new homologous series of azo-functionalised achiral bent-core compounds. The paper deals with the design, synthesis and liquid crystalline properties of four new homologous series of photochromic materials. In this study, we have investigated the effect of the presence of –N=N– linkage at different locations of the molecular architecture, on the mesomorphic properties. The molecular structures of all the newly synthesised compounds are established using the organic spectroscopic methods. The liquid crystalline properties are investigated using polarising optical microscopy (POM), differential scanning calorimetry (DSC), X-ray diffraction and electro-optical studies. They exhibit B₁ (col_r) and B₂ (SmC_AP_A) mesophases. We find that the presence of the –N=N– linkage at different locations in the molecular architecture does not seem to have much effect on the mesogenic behaviour of such compounds. However, we clearly see a profound effect of the location of the –N=N– linkage on the photo-induced electro-optical properties of these compounds.     

Liquid crystalline analogues of curcumin

Compounds that are modifications of curcumin were synthesised and their mesogenic properties were studied. The central keto-enolic ring in curcumin was replaced by either a pyrazole or an isoxazole ring. This gives compounds that can form liquid crystalline phases. When two alkoxy chains are attached to the molecule, nematic and lamellar phases appear; in the case of six alkoxy chains, a hexagonal columnar phase is created. The columnar phase is constructed from columns that in the cross-section have two molecules. The pyrazole derivatives in the columnar phase preserve N–H–N hydrogen bonding.     

Azomesogens with polar chloro,nitro and phenolic –OH substituents

Two new mesogenic homologous series containing chloro, nitro and phenolic hydroxy groups were synthesised and their molecular structures characterised by a combination of element analysis and standard spectroscopic methods. The mesomorphic behaviour of the compounds of both series was investigated by polarising optical microscopy and, in some cases, differential scanning calorimetry. All the compounds of both the series exhibit an enantiotropic nematic mesophase. In series I higher members also exhibit an enantiotropic smectic A (SmA) mesophase, whereas in series II the enantiotropic SmA mesophase commences somewhat earlier for the middle members. The mesomorphic properties of both series are compared with each other and also with the properties of other structurally related series to evaluate the effects of different polar substituents on mesomorphism.     

Synthesis of new wide nematic diaryl-diacetylenes containing thiophene-based heteromonocyclic and heterobicyclic structures,and their birefringence properties

New monocyclic and bicyclic thiophene-based diaryl-diacetylene liquid crystal (LC) materials were synthesised and demonstrated to exhibit wide enantiotropic nematic phases. One thiophenyl-benzene derivative, in particular, displayed a stable nematic phase across a temperature range of over 100°C. The birefringence properties of the compounds were measured using a multiple-beam interference (MBI) method, with the highest value found to be for the same thiophenyl-benzene molecule (Δn = 0.57, 550 nm) at 10°C above the crystal-to-nematic transition temperature. Furthermore, the effects of the cyclic structure on the mesomorphic behaviours, transition temperatures, and birefringence properties were investigated in detail from both experimental and theoretical viewpoints.     

The first examples of room temperature liquid crystal dimers based on cholesterol and pentaalkynylbenzene

In this article, we report the synthesis of the first examples of room temperature liquid crystal dimers based on cholesterol and pentaalkynylbenzene linked via flexible alkyl spacers. The thermal behaviour and mesomorphic properties of the newly synthesised compounds were investigated by differential scanning calorimetry, polarised optical microscopy and X-ray diffraction studies. All the synthesised dimers showed nematic (N*) phase at room temperature and exhibited excellent fluorescent emission properties. The steady-state anisotropy and fluorescence lifetime were measured in order to gain further insights into the supramolecular arrangement of these dimers.     

Geometric aspects influencing N-NTB transition - implication of intramolecular torsion

Herein we report a comprehensive study on novel carbonyl- and ethenyl-linked symmetric dimers that combine synthesis, mesomorphic properties and molecular modelling. The study has been focused on the impact of geometry imposed by the linkage group on the incidence of the twist-bend nematic (N_TB) phase. Comparison of the mesomorphic properties of these two series complemented with computational studies of conformational space around the linkage group points molecular curvature and intramolecular torsion plays important role in the appearance of the N_TB phase and can be regarded as the basic structural requirements for design of new twist-bend nematogen materials.     

New liquid crystals derived from thiophene connected to the 1,2,3-triazole heterocycle

In this work, six new compound derivatives from thiophene were synthesised. The three symmetrical compounds were synthesised containing two heterocyclic 1,2,3-triazole on each side of thiophene, 2,5-disubstituted and the three non-symmetrical compounds were synthesised containing alkyne groups as a spacer in replacing one of these heterocycles. The structural modifications were made by changing the number of alkoxy groups in order to understand the relation between structure and mesomorphic behaviour. Some of the compounds presented liquid crystalline properties, smectic and nematic mesophases. The non-symmetrical compounds allowed for a low emission in the blue region.     

Synthesis and mesomorphic properties of four ring,rod-like fluorene derivatives – the influence of the lateral substitution on mesomorphic properties of 2,7-bis(4-alkylphenyl)-fluorenes

ABSTRACT

This work presents new rod-like compounds being fluorene derivatives linked with other parts of the core at 2 and 7 positions – its synthesis and properties. The fluorene moiety is located in the central position of the four rings molecular core. The chain system in most cases was symmetrical and limited to pentyl or hexyl chains. To study the influence of the lateral substituents on mesomorphic properties two types of substituents have been incorporated, centrally located various short alkyl groups at fluorene’s 9,9 positions and outer core fluorosubstitutions located at side phenyl rings. All synthesised compounds exhibit liquid crystalline properties, where for laterally non-substituted and fluorosubstituted derivatives the dominant phases are smectics, while the nematics phases (nematic and chiral nematic – observed mostly on cooling cycle) occurs for compounds having alkyl substituents at 9,9 positions of fluorene. The synthetic methodology and mesomorphic properties of title compounds will be presented in detail as well as photophysical properties such as UV-visible absorption spectra and fluorescence spectra.     

The effect of intermolecular actions on the nematic phase range of tolane-liquid crystals

An approach to understand the effect of intermolecular actions on the nematic stability, a series of tolane compounds nH containing intermolecular π–π stacking, dipole–dipole and hydrogen bond interactions, are developed and investigated. Their mesophase behaviour were measured by differential scanning calorimetry (DSC) and polarising optical microscopy (POM), the results show that carboxylic acids nH exhibit high melting points and narrow nematic phase intervals, which are attributed to the too strong intermolecular actions. By disrupting the intermolecular hydrogen bond, their corresponding methyl esters nC have been designed and synthesised. It is interesting to note that these compounds exhibit broad nematic mesophase intervals and low melting points. The above results demonstrate that the interruption of intermolecular actions is an effective way to improve the nematic stability. In addition, the effects of the terminal alkyl chains and the terminal polar groups on the nematic stability were also discussed. Finally, DFT calculations of molecular conformation and dipole moment were conducted to better understanding of the molecular structure–mesomorphic property relationship.     

Synthesis,characterisation and liquid crystalline properties of some Schiff base-ester central linkage involving 2, 6- disubstituted naphthalene ring system

Four new mesogenic homologous series, each containing a 6-alkoxy 2-naphthoic acid and Schiff base-ester as central linkage, have been synthesised by esterification of 4-{[(4-hydroxyphenyl) imino] methyl} phenyl 4-propoxy benzoate, 4-{[(4-hydroxyphenyl) imino] methyl} phenyl 4- (pentyloxy) benzoate, 4-{[(4-hydroxyphenyl)imino]methyl}-2-methoxyphenyl 4- nitrobenzoate and 4-{[(4-hydroxyphenyl)imino]methyl}-2-methoxyphenyl 4- chlorobenzoate with different 6-alkoxy 2-naphthoic acid to give Series-A, -B, -C and -D, respectively. These compounds were characterised by elemental analysis, Fourier transform infrared, ¹H nuclear magnetic resonance, ultraviolet-visible and mass spectral studies. Their mesomorphic behaviour was studied by polarising optical microscope (POM) with a heating stage. POM data were compared with differential scanning calorimetry thermograms. In Series-A and -B all compounds exhibit mesomorphism. Series-A compounds exhibit a enantiotropic nematic mesophase, while a smectic A mesophase is observed from the butoxy derivative and persists up to the last member of the homologou series. Series-B compounds also exhibit the enantiotropic nematic mesophase, while the smectic A mesophase is observed from the ethoxy derivative and persists up to the last member of the homologou series. The mesomorphic properties of both series are compared with each other and the other structurally related Series-C and –D compounds. In Series-C and -D all compounds exhibit the only nematic mesophase; no smectic mesophase is observed even for higher members of the homologous.

The aim of the research was to synthesise and characterise novel liquid crystalline compounds containing 2,6-disubstituted naphthalene and to study their mesomorphic properties.     

Azo compounds and Schiff 's bases derived from 5-(4-pyridyl)-2-amino-1,3,4-thiadiazole: synthesis, mesomorphic properties and structural study by semi-empirical calculations

The synthesis and liquid crystalline properties of new Schiff 's bases (series 3a-f) and azo compounds (4a-f) incorporating pyridine and 1,3,4-thiadiazole rings are reported. The first homologues in the series of Schiff's bases (3a-c) show a monotropic mesophase and the homologues 3d-f display an enantiotropic SmA phase. The only azo compounds to exhibit liquid crystalline properties are the homologues 4e, f which show a monotropic nematic phase. These series are compared with Schiff's bases and azo compounds analogues (series 5 and 6), previously reported by us and an AM1 study of the structure/mesomorphic property relationship is described.     

Thermally stable azo-substituted bent-core nematogens: observation of chiral domains in the nematic mesophases composed of smectic nano clusters

In an effort to synthesise thermally stable bent-core nematogens with fairly low transition temperatures and wide nematic mesophase range, we have synthesised five new series of azo-substituted bent-core compounds without Schiff’s base unit. Here, we studied the effect of different lateral substituents (–CH₃ and –Cl), at two different positions in one of the arms, on the mesogenic properties. We found that such variation in the molecular architecture has a clear-cut impact on the transition temperatures as well as the liquid crystalline properties. The mesogenic properties of these compounds were studied using polarising optical microscopy and differential scanning calorimetry. The exact nature of different mesophases is investigated using X-ray diffraction studies. The results obtained indicated the presence of smectic nano clusters in the nematic mesophases of these compounds. We observed domains of opposite handedness in these nematic phases. The unusual properties of these mesophases were investigated by electro-optical studies. The electro-convection pattern study showed that these nematic mesophases are of negative dielectric anisotropic in nature. The compounds synthesised here exhibit photo-switching both in solution and in their nematic mesophases, a property that can be exploited for practical applications.     

Spectroscopic study of liquid crystalline N-[4-(4-n-alkoxybenzoyloxy)2-hydroxybenzylidene]hydroxyanilines

New homologous series of N-[4-(4-n-alkoxybenzoyloxy)-2-hydroxybenzylidene]hydroxyanilines were synthesized. All 4-hydroxyaniline derivatives exhibited a nematic phase, while 3-hydroxyaniline and 2-hydroxyaniline derivatives exhibited only a nematic phase as the terminal alkoxy group was lengthened. Infrared spectra suggest that the 4-hydroxyaniline derivatives form intermolecular hydrogen bonding of the single bridge type, while the 3-hydroxy and 2-hydroxy derivatives form the polymer type. The Raman band at around 1360 cm^-1 exhibited large differences in intensity among these derivatives. This can be explained by the effect of intermolecular or hydrogen bonding molecular conformation.     

Chiral smectogens with four-phenyl-ring molecular core,laterally substituted by iodine atom

Two series of lactic acid derivatives, based on four-ring molecular core laterally substituted by iodine atom, have been synthesised and their liquid crystalline properties studied. The non-chiral chain length has been varied and its influence on mesomorphic properties studied. All new compounds reveal the SmA*-SmC* phase sequence in an extremely broad temperature interval. The experimental techniques, namely the polarising optical microscopy, DSC, X-ray diffraction and helical pitch measurements, have been applied to establish the physical properties. New materials denoted JFRm/6 and JFRm/MB (with varying m as a number of carbon atoms in the non-chiral chain) are compared with the previously synthesised analogues (non-substituted and laterally substituted by a different halogen atom, namely bromine and chlorine).     

New highly anisotropic liquid crystal materials for high-frequency applications

We report on the developed liquid crystal (LC) compositions with large optical anisotropy and low melting point on the basis of synthesised quaterphenyl and quinquiphenyl LC compounds containing lateral substituents. Optical and dielectric anisotropies of synthesised compounds were studied to select the most optimal compounds for high-frequency applications. As a result of the research, base matrices with a wide range of the nematic phase were developed and their mesomorphic and physicochemical properties were investigated. Based on the experimental data, the influence of various fragments of molecules on the magnitude of permittivity in the high-frequency region, as well as on the loss tangent of LCs was established.     

New liquid crystals containing the benzothiazol unit: amides and azo compounds

Two series of calamitic liquid crystals containing a benzothiazole ring within the central core and two different linkage groups (amide and azo) have been prepared and their liquid crystalline properties studied and compared with those of the analogous series of imines. The influence of the linkage group within the central core has been proven to determine the variety of mesomorphism displayed by the compounds. The compounds with imine and azo linkages behave in a similar way and exhibit typical nematic and smectic C mesophases. Compounds incorporating an amide linkage show a poorer mesomorphism and mainly present a smectic C mesophase.