The influence of lateral substituents on the phase behaviour of nematogenic liquid crystals

The influence of lateral substituents or side chains attached to thermotropic nematogens is considered on the basis of the Flory lattice model. The rigid core of the nematogen is characterized by its axial ratio x and the characteristic temperature T* which measures the strength of the anisotropic dispersion forces operative between the cores. For the side chain an additional parameter zm which is proportional to its hard core volume enters the partition function. Given these quantities and the free volume as obtained from the thermal expansion coefficient, the nematic-isotropic transition temperature T_NI and the temperature dependence of the order parameter may be calculated. The results show that the lowering of T_NI by lateral substituents is caused by (1) their interference with molecules packing and (2) the dilution of the anisotropic dispersion forces between the central nematogenic cores. As an additional consequence of this the order parameter is lowered considerably. A survey of recent experimental data shows that the decrease of T_NI is correlated solely with the hard core volume of the substituent regardless of its chemical structure or polarity, thus corroborating the theoretical predictions.     

The synthesis and mesomorphic behaviour of tetracatenar di-hydrazine derivatives

Symmetrical four-chained (tetracatenar) di-hydrazine derivatives, namely oxalyl N',N'-bis(3,4-dialkoxybenzoyl)-hydrazide (BFH-n, n?=?4, 6, 8, 10), were synthesised. Investigations on the liquid crystalline properties by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and polarising optical microscopy (POM) showed that the di-hydrazine derivatives exhibited columnar mesophases and the symmetry of the mesophase changes from rectangular to hexagonal on increasing the temperature. The rectangular columnar mesophases of BFH-n (n?=?6, 8, 10) remained stable down to 10°C during cooling and the subsequent recrystallisation from the Col_r phase of BFH-n (n?=?6, 8, 10) was observed on the second heating runs. Furthermore, the average number of molecules packing in a column slice was estimated to be three, based on their X-ray diffraction results. Intermolecular hydrogen bonding between –C=O and ?N?H groups in crystalline and liquid crystalline phases was confirmed.     

Synthesis and mesomorphic properties of chiral swallow-tailed thioester liquid crystals with lateral substituents

Two homologous series of chiral swallow-tailed thioester materials, 1-ethylpropyl (R)-2-[3-fluoro-4-(4'-alkyloxybiphenylcarbonylthio)phenoxy]propionates, I-6 (m = 8-12), and 1-ethylpropyl (R)-2-[3-methyl-4-(4'-alkyloxybiphenylcarbonylthio)phenoxy]propionates, II-6 (m = 8-12), have been synthesized and their mesomorphic phases studied. The results show that materials I-6 (m = 8-12) with a fluoro substituent, display the phase sequence I-BPII-N*-SmC*-Cr, whereas materials II-6 (m = 8-12) with a methyl substituent display the phase sequence I-N*-TGBA*-SmA*-Cr during cooling. The physical properties of the SmC* phase in materials I-6 were measured. The results show that the maximum P _s values are in the range 91-95 nC cm^-2 and the maximum tilt angles are about 34-37°.     

Synthesis and mesomorphic behaviour of novel light-emitting liquid crystals

We report the results of a systematic study of the structure-mesomorphic behaviour relationships of a diverse range of light-emitting liquid crystals, but especially nematic 2,7-disubstituted-9,9-dialkylfluorenes. The dependence of the mesomorphic behaviour and transition temperatures on the nature and length of the terminal chains, the nature, position and number of lateral substituents and the number and nature of aromatic rings with and without heteroatoms in the central core is studied. The results of these studies are used to design polymerizable, light-emitting crystals (reactive mesogens) with a nematic phase having a high clearing point and a melting point below room temperature for facile OLED fabrication.     

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.     

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.     

The effect of a lateral methoxy group on the mesomorphic properties of ferroelectric liquid crystals

A new series of ferroelectric liquid crystal materials having the methoxy group substituted in an aromatic ring of the mesogenic core has been synthetized and characterized. This electron-donor methoxy group makes the ferroelectric S*_c phase narrower in range and monotropic when compared to the series with the unsubstituted molecules, the values of the spontaneous polarization remaining unaffected.     

Synthesis and mesomorphic behaviour of unsymmetrical tetracatenar [1,2,3]-triazole derivatives

New nonsymmetric four-chained and three-chained [1,2,3]-triazole derivatives were synthesised. Their phase behaviours were investigated by differential scanning calorimetry, polarised optical microscopy and X-ray diffraction analyses. The tetracatenar derivatives show a columnar mesophase and a lamellar crystalline phase. The effects of the length of the terminal alkoxy chain and the nature of the terminal group attached to the side phenyltriazole unit of the mesogenic core are discussed.     

Schiff base/ester liquid crystals with different lateral substituents: mesophase behaviour and DFT calculations

Four new groups of 4-((2?-substitutedphenylimino)methyl)phenyl-4”-alkoxy benzoates, In_a-d, of Schiff base ester liquid crystals, were prepared and investigated for their mesophase formation and stability. Each group constitutes four homologous series that differ from each other by the lateral attached polar group X in the ortho position for the imine mesogen at terminal benzene ring that alternatively changed from F, Br, NO2 and lateral benzene ring. Within each homologous series, the number (n) of carbons in the alkoxy chain varies between 6, 8, 10 and 12. Molecular structures of the prepared compounds were confirmed via elemental analysis, FT-IR, and ¹H NMR spectroscopy. Mesomorphic properties were investigated by differential scanning calorimetry (DSC) and the phase identified by polarised light microscopy (PLM). A comparative study was made between the investigated compounds and their previously prepared laterally neat, 4-((4?-phenylimino)methyl)phenyl-4”-alkoxy benzoates (IIn); the result revealed that all lateral substituents not only decrease the melting temperature but also the mesophase stability and shown only nematic phase. Density functional theory (DFT) calculations for new lateral derivatives were discussed.     

Effect of lateral methoxy substitution on mesomorphic and structural properties of ferroelectric liquid crystals

A new series of materials with a chiral fragment derived from lactic acid and a methoxy group as lateral substituent in different positions of the molecular core was synthesised and investigated. Derivatives with ester or ether linkages of the non‐chiral chain were also studied. Depending on the molecular structure, cholesteric, twist grain boundary smectic A (TGBA*), chiral smectic A (SmA*) or chiral smectic C (SmC*) phases were detected. In derivatives with the ester linkage and a methoxy group at the nearest and the next nearest phenyl ring to the non‐chiral chain these phases completely disappear. On the other hand, a methoxy group on the phenyl ring close to the chiral chain provides a compound with low layer shrinkage at the SmA*–SmC* phase transition (“de Vries” behaviour). The temperature dependence of the spontaneous polarisation, the tilt angle, the layer spacing as well as the complex permittivity were studied and the results discussed in terms of molecular structure.     

Synthesis and mesomorphic behaviour of wedge-shaped nematic liquid crystals with flexoelectric properties

The synthesis and mesomorphic behaviour of a series of wedge-shaped liquid crystals and some reference compounds are reported. These unusual liquid crystals possess smectic C, smectic A and nematic phases. These new wedge-shaped materials with a high degree of shape anisotropy and a large dipole moment can be used to induce an increase in the flexoelectric effects of nematic guest-host mixtures as dopants at low concentrations.     

High tilt antiferroelectric esters bearing a perfluorobutanoyloxy terminal chain: the influence of lateral fluoro substituents on mesomorphic behaviour, tilt angle, and spontaneous polarization

Novel liquid crystalline esters have been synthesized with a perfluorocarbonyloxy terminal chain and lateral fluoro substituents in order to determine their influence on mesomorphic behaviour, tilt angle and spontaneous polarization. Certain locations of lateral fluoro substituents provide for very low melting points and reasonably wide temperature ranges of the antiferroelectric phase, and can generate enhanced tilt angles of up to 45°, although spontaneous polarization is always lower than for the parent system without lateral fluoro substituents. Thus, these novel materials, particularly as components in mixtures, should be useful in high tilt antiferroelectric (orthoconic) applications.     

The interplay of bent-shape,lateral dipole and chirality in thiophene based di-, tri-, and tetracatenar liquid crystals

A range of mesogenic molecules varying in both bend angle and strength of lateral dipole were synthesized, and their phase behavior was characterized by polarizing microscopy, thermal analysis, X-ray diffraction, and electrooptical measurements. We find the general destabilization of the liquid crystallinity caused by strong lateral dipolar groups and the bent molecular shape are off-set in mesomorphic tetracatenars, which display stable nematic, smectic, columnar, and cubic mesophases. The broad mesomorphism of the tetracatenars containing lateral dipoles and their incompatibility with chiral induction are explained by considering that loosely correlated dimers exist within the mesophases. Chiral mesophases of derivatives with strong lateral dipoles were achieved by attaching fewer or different side chains to each end of the mesogen.     

High tilt antiferroelectric esters bearing a perfluorobutanoyloxy terminal chain: the influence of lateral fluoro substituents on mesomorphic behaviour,tilt angle,and spontaneous polarization

Novel liquid crystalline esters have been synthesized with a perfluorocarbonyloxy terminal chain and lateral fluoro substituents in order to determine their influence on mesomorphic behaviour, tilt angle and spontaneous polarization. Certain locations of lateral fluoro substituents provide for very low melting points and reasonably wide temperature ranges of the antiferroelectric phase, and can generate enhanced tilt angles of up to 45°, although spontaneous polarization is always lower than for the parent system without lateral fluoro substituents. Thus, these novel materials, particularly as components in mixtures, should be useful in high tilt antiferroelectric (orthoconic) applications.     

The effects of lateral halogen substituents on the low-temperature cybotactic nematic phase in oxadiazole based bent-core liquid crystals

We have previously demonstrated that the incorporation of lateral methyl groups on oxadiazole-based liquid crystals leads to relatively low-temperature cybotactic nematic phases which, in some cases, supercool to room temperature. We report here the synthesis and phase behaviour of related compounds that possess lateral halogen groups and in some cases, lateral methyl groups as well. Derivatives with three lateral substituents (one halogen and two methyl groups) in a specific pattern supercool in the nematic phase to room temperature. As was the case with the previously reported trimethylated derivatives, the low-temperature nematic phase is glassy in nature. Two of the new trisubstituted derivatives (with bromo and chloro groups) remain in the nematic phase upon subsequent heating until transitioning to the isotropic phase indicating that the low-temperature nematic phase may be more stable than that shown by the trimethylated analogue. Preliminary X-ray diffraction analysis confirms the presence of a tilted cybotactic nematic phase. In addition, the splitting observed in the wide-angle scattering feature is indicative of enhanced local biaxial packing.     

Synthesis and mesomorphic properties of benzoxazole derivatives with lateral multifluoro substituents

Fluorinated aromatics is generally chosen as mesogenic cores to design novel liquid crystal compounds. Here, a series of benzoxazole derivatives with laterally multifluorinated biphenyl units, 2-(3′,3-difluoro ?4′-alkoxy-1,1′-biphenyl-4-yl)-benzoxazole derivatives (coded as nPF(3)PF(3)Bx), are synthesized and characterized, where methyl and nitro moieties are selected as terminal groups to investigate the effects of different polar substituents on the liquid crystal properties. The compounds nPF(3)PF(3)Bx show enantiotropic mesophases with mesophase ranges of 0–40°C and 0–63°C on heating and cooling for hydrogen-terminated derivatives (nPF(3)PF(3)BH), 43–93°C and 54–123°C for methyl-terminated ones (nPF(3)PF(3)BM), 60–108°C and 74–152°C for nitro terminated ones (nPF(3)PF(3)BN), respectively. They exhibit photoluminescence emission peaks at 390–392 nm and UV–vis absorption bands with maxima at 327–330 nm, respectively. The results reveal that lateral multifluoro substituents lead to a decrease in melting/clearing points, while electron-withdrawing terminal nitro moiety results in increases in both melting point and mesophase range.     

Cholesterol-based dimeric liquid crystals: synthesis,mesomorphic behaviour of frustrated phases and DFT study

Chiral unsymmetrical dimeric liquid crystals consisting of a cholesterol moiety as chiral entity and a substituted salicylidene imine core (with the substituent being butyl or fluoro or chloro group) interconnected through an even methylene spacer have been synthesised and their mesomorphic properties are characterised. All the dimers exhibit enantiotropic mesophases. The butyl homologue exhibited N* phase only, the fluoro- and chloro-substituted compound exhibited frustrated blue phases (BPs), N* phase and SmC* or twisted grain boundary (TGB) phases. The occurrence of a fluid frustrated phase, the BP, in particular, observed in compounds with a polar moiety and bent optimised conformation by density functional theory (DFT) study, indicates the importance of polar structures and bent shape of the compounds. Theoretical calculation was performed in order to study the optimised conformation, polarity and electron density distribution of the synthesised cholesterol derivatives using DFT. Time-dependent density functional theory (TD-DFT) calculation also had been carried out to investigate the absorption spectra and HOMO–LUMO energies. The experimental and theoretical absorption spectra are also presented.     

The effect of a lateral substituent on the mesomorphic properties in a series of ferroelectric liquid crystals with a 2-alkoxypropionate unit

A new series of ferroelectric liquid crystal materials containing a lateral methyl group on the aromatic ring of the alkoxybenzoate unit has been synthesized and investigated. These materials exhibit a wide temperature range of ferroelectric SmC* phase on cooling (including supercooling) with a very high spontaneous polarization. All phase transition temperatures are lower when compared with those of similar non-substituted materials. In comparison with the compounds containing the lateral methoxy group, only the SmC*-Cr transition changed significantly. The values of spontaneous polarization are mostly increased compared with both non-substituted and methoxy substituted compounds.     

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 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.