The effect of the alkyl chain length on the mesomorphic properties of new lactic acid derivatives

New series of lactic acid derivatives with alkyl terminal chain have been synthesised and their mesomorphic properties studied. We have varied the length of chiral and non-chiral terminal alkyl chains and found that prolonging both chains has a strong effect on the SmA*–SmC* phase transition. Most of the new materials exhibit only paraelectric SmA* phase; for homologues with a longer non-chiral chain (m ≥ 10), the ferroelectric (SmC*) phase appears below the SmA* on cooling and persists down to a room temperature. The role of the chiral terminal chain in the molecule is quite opposite – only its short length supports the existence of ferroelectric phase. Additionally, a hexatic phase appeared below the SmA*–SmC* phase sequence for several homologues at low temperatures. All materials have been studied using standard experimental techniques (differential scanning calorimetry (DSC), texture observations, polarisation and tilt angle measurements, etc.). Liquid crystalline properties of new materials have been compared with the previously prepared and studied lactic acid derivatives.     

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.     

Synthesis and mesomorphic properties of new liquid crystalline stilbene derivatives containing vinyloxyalkoxy chains

New liquid crystalline stilbene derivatives containing vinyloxyalkoxy chains 1 (n=5, 7, 9, 11) have been synthesised. Their mesomorphic properties have been studied by polarising optical microscopy and differential scanning calorimetry. It is interesting to note that even their alcohol precursors showed liquid crystalline behaviour. The effect of terminal alkoxy chain length and UV irradiation on the mesomorphic behaviour is discussed.     

Cybotactic nematic phases of photoisomerisable hockey-stick liquid crystals

New five-ring hockey-stick liquid crystalline materials with 4-bromoresorcinol as the central core unit and an azobenzene-based side arm were synthesised and their mesophase behaviour was investigated by polarising optical microscopy, differential scanning calorimetry, X-ray diffraction and under a triangular wave electric field. Additional structural modification was done by introducing a lateral fluorine atom in the terminal ring of one of the side arms. It is found that regardless of the alkyl chain length or the lateral fluorine substitution, all of the prepared materials are liquid crystalline exhibiting nematic phases composed of cybotactic clusters of the SmC-type (N_CybC) in addition to a monotropic SmC phase for the longest homologue.     

Liquid crystalline behaviour of hydrazide derivatives containing alkoxyazobenzene

Two series of dissymmetric hydrazide derivatives containing alkoxyazobenzene with nitro terminal group and octyloxy terminal group, N-4-alkoxyphenyl-N′-4-((4-nitrophenyl)azophenyl) benzohydrazide (Bn-NO₂, n indicates the number of carbon atoms) and N-4-octyloxyphenyl-N′-4-((4-octyloxyphenyl)azophenyl) benzohydrazide (B8-B8), were designed and synthesised, and their liquid crystalline properties were investigated by means of differential scanning calorimetry, polarised optical microscopy and wide-angle X-ray diffraction. It was found that B8-B8 with octyloxy terminal chains displayed monolayer smectic C phase, whereas Bn-NO₂ with nitro terminal group displayed SmA_d phase, and intermolecular hydrogen bonding was confirmed as the driving force. In addition, the effect of hydrogen bonding, dipole–dipole interactions and steric hindrance effect on the liquid crystalline structures were also discussed.     

Hexagonal columnar mesophases of polycatenar para-phenylene connected bis-oxadiazole-based liquid crystals

In this article polycatenar liquid crystals containing two 1,3,4-oxadiazoles interconnected by a para-substituted benzene ring as the central linking unit and three alkoxy chains at each terminal have been synthesised, and investigated by polarising microscopy, DSC and XRD scattering. Molecules with medium chain length form exclusively hexagonal columnar liquid crystalline phases.     

Mesomorphic and photophysical behaviour of 1,3,4-oxadiazole based hockey stick reactive mesogens

New hockey stick mesogens derived from 1,3,4-oxadiazole as a bent-core unit have been synthesised. The molecules resemble hockey stick shape due to the presence of two arms containing a different number of phenyl rings attached with the 1,3,4-oxadiazole bending unit. The shorter arm of the molecule consists of one phenyl ring and 4-n-alkyloxy terminal chains whereas the long arm of the molecule possesses containing two phenyl rings which are linked via imine linkage and reactive 4-n-undecenyloxy as a terminal chain. The thermal stabilities of the newly synthesised compounds were carried out by thermogravimetric analysis (TGA). The mesomorphic behaviour was investigated by polarising optical microscopy (POM) and differential scanning calorimetry (DSC). All the compounds exhibit enantiotropic nematic phase along with smectic phases (SmA and SmC phases). Interestingly, the compounds with lower 4-n-alkyloxy terminal chains (n = 4 and 6) exhibit a wide range of optically isotropic DC phase. On increasing, the terminal 4-n-alkoxy chain length the DC phase disappears. The photophysical properties of the compounds were investigated in different solvents and in the solid state. It was observed that the compound exhibit absorption in UV region and emission in the green region.     

Synthesis of novel (-)-menthol-based azobenzene chiral liquid crystals and effect of terminal alkyl chains on mesomorphic behaviour

ABSTRACT

A series of novel azobenzene chiral liquid crystals (Mt4AZOnB) containing (-)-menthyl were successfully synthesised. Terminal alkyl chains of the molecules varied from methyl to hexyl. The chemical structures were characterised by Fourier transform infrared and ¹H-NMR spectra. Liquid crystalline behaviour of the chiral liquid crystals was characterised by differential scanning calorimetry and polarising optical microscopy. The effect of terminal alkyl chains on mesomorphic and photoisomerisation behaviour of azobenzene-based liquid crystals is discussed. The lower members (n = 1, 2, 3, 4) are monotropic and only the higher members (n = 5, 6) show enantiotropic behaviour. These compounds show a distinct odd-even effect for the phase transition temperature when the parity of the terminal chain is varied.     

Structure and photoconductive behaviour of a sanidic liquid crystal

A series of [1]benzothieno[3,2-b][1]benzothiophene-2,7-dicarboxylate derivatives consisting of a flat, conjugated aromatic moiety containing sulphur hetero-atoms and substituted by terminal chains - ethyl, decyl, Z-4-decenyl or 2-(2-butoxyethoxy)ethyl - has been synthesized. These materials exhibit a smectic liquid crystalline phase, the stability of which was found to be strongly dependent on the length and the nature of the terminal chains. In the mesophase, the molecular arrangement within the smectic layer is characterized by a local stacking of the rigid parts similar to that found in discotic columnar systems. Finally, clear photoconductive behaviour was found in mechanically aligned samples of these liquid crystals.     

Structure and photoconductive behaviour of a sanidic liquid crystal

A series of [1]benzothieno[3,2-b][1]benzothiophene-2,7-dicarboxylate derivatives consisting of a flat, conjugated aromatic moiety containing sulphur hetero-atoms and substituted by terminal chains - ethyl, decyl, Z-4-decenyl or 2-(2-butoxyethoxy)ethyl - has been synthesized. These materials exhibit a smectic liquid crystalline phase, the stability of which was found to be strongly dependent on the length and the nature of the terminal chains. In the mesophase, the molecular arrangement within the smectic layer is characterized by a local stacking of the rigid parts similar to that found in discotic columnar systems. Finally, clear photoconductive behaviour was found in mechanically aligned samples of these liquid crystals.     

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.     

Design,synthesis, and characterisation of symmetrical bent-core liquid crystalline dimers with diacetylene spacer

Two new symmetrical bent-core liquid crystalline dimers (B-DA4 and B-DA12) bearing diacetylenes spacer and different terminal alkyl chains were successfully synthesised via Sonagashira coupling reaction. The molecular structures of these dimers were confirmed by ¹H nuclear magnetic resonance (NMR), Fourier transform-infrared spectroscopy (FT-IR), Raman spectroscopy, mass spectrometry, and elemental analysis. Their thermal stability and liquid crystalline properties were characterised by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), polarised light microscopy (PLM), and small-angle X-ray scattering (SAXS). Results showed that the diacetylene group may be thermal polymerised at about 260°C far from thermal decomposition. The dimers exhibited monotropic phase behaviour and typical layered-structure phase with long-range order on a length scale of about 6.3 nm was observed. The results mentioned above offer a promising opportunity to design polydiacetylene nanowires by thermal, UV irradiation, or scanning tunnelling microscope (STM) tip-induced polymerisation.     

Synthesis and characterisation of 3-armed dendritic molecules with triphenylbenzene or triphenyltriazine as core and triphenylene derivative as shells

Two series 3-armed dendritic molecules with their 1,3,5-tris(4-methyloxyphenyl) benzene or 2,4,6-tris(4- hydroxylphenyl)-1,3,5-s-triazine core and triphenylene derivative shells connected by soft hydrocarbon chains have been synthesised and fully characterised. Whether liquid crystal (LC) or photoluminescence materials have been tuned by changing the length of the soft chain and they have been studied by POM, DSC, XRD, UV-Vis and PL. The results show that all the new dendritic compounds display UV to blue fluorescence in solvents such as DCM, THF and acetone. The TC3 compound bearing 1,3,5-tris(4-hydroxylphenyl) benzene core exhibits LC property with rectangular columnar phase (Col_r) on cooling.     

New mesogenic compounds possessing a biphenyl ester and ether moiety comprising 1,3-dimethylbarbituric acid: synthesis,characterisation and mesomorphic studies

New substituted derivatives of 5-vinyl-1,3-dimethylbarbituric acid were synthesised and evaluated for liquid crystal properties. Two sets of molecules were prepared. One end of all the molecules possesses the 1,3-dimethylbarbituric core. The first set comprises biphenyl ethers, 4a–n and the second set biphenyl esters, 5a–g. Liquid crystalline properties were investigated by POM and DSC techniques. All the compounds exhibited enantiotropic smectic A and nematic mesophases. The LC properties were found to depend on the spacer and terminal alkoxy- chain and alkoxy- ester moiety of the molecules. Smaller alkyl chain members showed a smectic phase, while higher alkyl chain members showed a nematic phase.     

Novel photo-crosslinkable liquid crystalline polymers containing vanillylidene cycloalkanones and azobenzene units

Two series of novel liquid crystalline photo-crosslinkable bis(vanillylidene-azobenzene) cycloalkanone containing polymers, namely poly(vanillylidene alkyloxy-4,4'-azobenzenedicarboxylic ester)s, have been synthesised from bis[m-hydroxyalkyloxy(vanillylidene)cycloalkanone] (m = 6, 8, 10) with azobenzene dicarbonylchloride by solution polycondensation method at ambient temperature. Polymers with varying spacer lengths have been synthesised and characterised by spectroscopic techniques. These variations have been correlated with the thermal properties and transition temperatures. Thermal transitions were analysed by differential scanning calorimetry (DSC) and the mesophases were identified by hot stage optical polarised microscopy (HOPM). All of the polymers were found to exhibit liquid crystalline properties. Transition temperatures were observed to decrease with increasing spacer length. The thermogravimetric analysis reveals that all of the polymers were stable up to 280°C undergo two-stage decomposition. Using the UV-visible photolysis studies we investigated the simultaneous behaviour of reactivity rates of crosslinking in the vanillylidene unit and isomerisation caused by the azobenzene unit in the photo-crosslinkable main chain liquid crystalline polymers. The photolysis of liquid crystalline bis(vanillylidene)cycloalkanone-based polymers reveals that there are two kinds of photoreactions in these systems: the EZ photoisomerisation of azobenzene unit and 2p+2p addition by vanillylidene units. The EZ photoisomerisation in the liquid crystal phase disrupts the parallel stacking of the mesogens, resulting in the transition from the liquid crystal phase to isotropic phase. The photoreaction involving 2p+2p addition of the bis(vanillylidene)cycloalkanone units in the polymers results in the conjoining of the chains. The cyclopentanone polymers exhibited a faster rate of photolysis than the cyclohexanone polymers.     

Chiral and orientationally ordered fluid mesophases formed by oxadiazole bisaniline based achiral bent mesogens

Development of new liquid crystalline materials exhibiting interesting properties and phases continues to be an enabling enterprise in the forward march of their successful display and non-display applications. The design and synthesis of a homologous series of liquid crystalline bent-core compounds derived from the oxadiazole bisaniline moiety and the phase behavior of three members of the series that exhibit nematic, smectic C, and dark conglomerate phases is reported. The liquid crystalline phases exhibited by these mesogens are characterized using polarized optical microscopy, differential scanning calorimetry and x-ray scattering techniques. All three homologs prepared exhibit the nematic phase. Interestingly, the homolog with short hexyl terminal chains exhibits only the nematic phase that is stable over a very broad, nearly 100 K wide, temperature range. The compound with terminal octyl chains shows the chiral dark conglomerate phase below the nematic phase despite the bent molecules being achiral. The homolog with dodecyl alkyl chains is found to possess the smectic-C and two additional lamellar phases besides the nematic phase. These compounds enrich the library of achiral bent-core materials capable of exhibiting chiral and nematic phases.     

Phenyl-cyclohexyl enaminoketone ligands and their Cu(II) complexes

The liquid crystalline properties of 1-(alkylamino)-3-[(4'-hexyl-trans-cyclohexyl-4'-phenyl]-prop-1-en-3-one-s, from methyl to octadecyl, and their copper (II) complexes have been examined by optical, DSC, X-ray and EPR methods. The compounds are enantiotropic nematogens except those having the shortest and the longest terminal chains. Short chains promote the S_A phase in both ligands and complexes, whereas long chains promote S_C and crystal H phases for the ligands or S_A and S_C phases for the complexes. A partly bilayer smectic A_d phase is observed from ligands terminated with short non-polar substituents. Direct isotropisation from the crystal H phase for some of the compounds, as well as other phase transitions have been studied. The molecular shape of the complexes and the organization of their mesomorphic phases are discussed, based on the refractive indices and X-ray data.     

Supermolecular liquid crystals with a six-armed cyclotriphosphazene core: from columnar to cubic phases

New liquid crystals having a non‐conventional structure have been synthesised from a six‐armed cyclotriphosphazene core, [N₃P₃(OC₆H₄OH‐4)₆], which was condensed with polycatenar acids. Reactions were monitored by ³¹P{¹H} and ¹H NMR spectroscopy and the chemical structure of the resulting materials was confirmed by different spectroscopic techniques and mass spectrometry (MALDI‐TOF). Results were in accordance with monodisperse, fully functionalised cyclotriphosphazenes. Thermal and mesomorphic properties were studied by optical microscopy, differential scanning calorimetry and X‐ray diffraction. All of the synthesised phosphazenes, substituted with benzyl ether chains, show a high thermal stability and exhibit mesomorphic properties, which depend on the number and type of alkyl terminal chains located at the periphery of the mesogens. Mesomorphic properties range from Col_h for cph‐A1 and cph‐A2 to a cubic phase detected for cph‐A3 , which has the larger number of alkyl chains. Furthermore, helical order was detected on X‐ray data of cph‐A2 , which has chiral branched chains. Circular dichroism spectra of annealed films at mesophase temperature show a signal attributed to the chiral helical arrangement of the mesogenic chromophores.     

Synthesis,mesomorphic, photophysical and computational studies of new achiral four-ring unsymmetrical bent-core mesogens and their Copper(II) complexes

New achiral four-ring unsymmetrical bent-core mesogens derived from 2,5-dihydroxybenzaldehyde and their copper(II) complexes have been synthesised as a new design with an imine and ester linkage. These new bent-core molecules resemble hockey-stick shape, which possesses 4-n-alkyloxy chain (4-n-hexyloxy and 4-n-decyloxy) at one end and methyl or methoxy group at the other end of the molecule. The synthesis, spectroscopic characterisation, phase transition temperature and characterisation of phase behaviour are reported. The bent-core molecules exhibited monotropic nematic and smectic A phase depending on the terminal chain length. Interestingly, copper(II) complexes of bent-core molecules displayed monotropic nematic phase. This is the first report on copper(II) complexes of bent-core molecules that exhibited nematic phase. The four-ring bent-core molecule exhibited fluorescence with large stoke shift. The density functional theory calculations of bent-core molecules and their copper(II) complexes are carried out using Gaussian 09 program at B3LYP level to obtain the stable molecular conformation, dipole moment, highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energies and bending angle of the compounds. The natural atomic charges and electronic configurations of the atoms of free ligands as well as the complexes have been evaluated.     

Novel photo‐crosslinkable liquid crystalline polymers containing vanillylidene cycloalkanones and azobenzene units

Two series of novel liquid crystalline photo‐crosslinkable bis(vanillylidene‐azobenzene) cycloalkanone containing polymers, namely poly(vanillylidene alkyloxy‐4,4′‐azobenzenedicarboxylic ester)s, have been synthesised from bis[m‐hydroxyalkyloxy(vanillylidene)cycloalkanone] (m = 6, 8, 10) with azobenzene dicarbonylchloride by solution polycondensation method at ambient temperature. Polymers with varying spacer lengths have been synthesised and characterised by spectroscopic techniques. These variations have been correlated with the thermal properties and transition temperatures. Thermal transitions were analysed by differential scanning calorimetry (DSC) and the mesophases were identified by hot stage optical polarised microscopy (HOPM). All of the polymers were found to exhibit liquid crystalline properties. Transition temperatures were observed to decrease with increasing spacer length. The thermogravimetric analysis reveals that all of the polymers were stable up to 280°C undergo two‐stage decomposition. Using the UV–visible photolysis studies we investigated the simultaneous behaviour of reactivity rates of crosslinking in the vanillylidene unit and isomerisation caused by the azobenzene unit in the photo‐crosslinkable main chain liquid crystalline polymers. The photolysis of liquid crystalline bis(vanillylidene)cycloalkanone‐based polymers reveals that there are two kinds of photoreactions in these systems: the EZ photoisomerisation of azobenzene unit and 2p+2p addition by vanillylidene units. The EZ photoisomerisation in the liquid crystal phase disrupts the parallel stacking of the mesogens, resulting in the transition from the liquid crystal phase to isotropic phase. The photoreaction involving 2p+2p addition of the bis(vanillylidene)cycloalkanone units in the polymers results in the conjoining of the chains. The cyclopentanone polymers exhibited a faster rate of photolysis than the cyclohexanone polymers.