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Four series of di-flouro, namely; 4-substituted phenylazo-3-flouro phenyl-4′-n-alkoxy 3-flouro phenylazo benzoates (Ina-d) based on aromatic rings with the azo/ester/azo linkages core, were prepared and investigated for their mesomorphic properties. An alkoxy group with chain length varied from n = 6 to 16 is attached to the terminal phenylazobenzoate moiety and the other terminal is a compact group (X = –CH3O, –CH3, H and Br) attached to phenylazo moiety. The mesophases were investigated by DSC and POM and compared with previously investigated dilaterally methyl substituted analogues. Terminally unsubstituted and Br substituted analogues displayed dimorphic N and SmA phases, except the lower homologue (n = 6), while terminally – CH3O analogues exhibited monomorphic N phase. For terminally – CH3 substituted, compounds with n = 6–12 exhibited only N phase, while compounds with n = 14 and 16 displayed N and SmA phases. Meanwhile, the dilateral F substituents result in an enhancement in clearing thermal transitions compared with dilateral methyl substituents with a wide mesophase range. TGA analysis revealed that the prepared compounds are thermally stable within mesophase temperature range, except – CH3O, –CH3 and Br derivatives with n = 6. Binary mixtures of I6a-d/I16a-d derivatives were investigated. The photo-physical property was also studied.

In the present work two homologue series of four-ring azo/ester/imine compounds; namely, 4-(4′–alkoxy–phenylazo) phenyl–4′′–(benzylidene–amino) benzoate, In, and 4–(4′–alkoxy–phenylazo) phenyl–4′′–[(pyridin-3–ylmethylene)–amino] benzoate, IIn, were prepared and investigated for their mesophase behaviour. In these two types of homologue series, the length of the terminal alkoxy group (n) varies between 6 and 16 carbons. Compounds prepared in both series were structurally characterised via thermogravimetric and elemental analyses, FTIR, 1H-NMR, and mass spectroscopy. Their mesophase transition temperatures were determined by differential scanning calorimetry (DSC), whereas, the type of the mesophase was identified by polarised light microscopy (PLM). The molecular structure–property relationship was conducted aiming to investigate the effect of replacing the terminal phenyl group in In with a pyridyl one in IIn, in addition to the effect of variation of the alkoxy chain length. Aiming to investigate the effect of inversion of the methineazo group on the mesophase behaviour of the compounds, a comparison was made between the prepared series of compounds (In) with previously prepared four rings 4-(4′-alkoxyphenylazo)–phenyl 4′′–phenyliminomethyl–benzoate phenyl-4ʹ-(4′′-alkoxyphenylazo) benzoate, IIIn. Finally, the mesophases of series IIn were compared with their corresponding three-ring analogues, 4-(4′-alkoxy phenyl −4′′-[(pyridin-4-ylmethylene)–amino] benzoate analogues (IVn).

In order to investigate the effect of replacing the azo group with the azomethine in the previously investigated four-ring azo/ester/azo compounds, 4-alkoxy phenylazo phenyl 4ʹ-(4′′-alkoxyphenylazo...

Twenty four different homologues of the formula 4-alkoxy phenylazo phenyl 4ʹ-(4''-alkoxyphenylazo) benzoates (Im/n) were prepared and investigated for their mesophase behaviour. In these compounds,...

Two homologous series of the three-ring 4ʹ-(4"-alkoxy-2"-(or 3")fluoro phenylazo) benzoates terminated with 2-(or 1-) naphthyl groups (Ind&e or IInd&e), respectively, were prepared and thei...

New three groups of 2-hydroxypyridine ester-based liquid crystals named, 5-[2-(4-substitutedphenyl)diazenyl]pyridin-2-yl 4ʹ-alkoxybenzoate were synthesised. Each group differs from each oth...

Two homologous series of the three-ring azo/ester compounds 2-(or1-) naphthyl 4ʹ-(4ʹ’-alkoxy phenylazo) benzoates (Ina and IIna) were synthesised. A lateral methyl group was introduced in different positions of the alkoxy phenyl moiety, in position-2 to give series Inb and IInb and in position-3 to give series Inc and IInc. Molecular structures were characterised via elemental analyses, infrared and 1H-NMR. Their mesophase characteristics were investigated by differential scanning calorimetry (DSC) and their phases identified via polarised light microscopy (PLM). Transition temperatures were correlated with the alkoxy-chain length (n) that varies between 6, 8, 10, 12, 14, and 16 carbons. Comparative studies were first made to investigate the effect of including the extra fused benzene ring, and its orientation, into the previously investigated three-ring compounds, 4-phenyl 4ʹ-(4′′-alkoxyphenylazo) benzoates (IIIna). Investigation of the mesophase behaviour was extended to cover the effect of introducing the lateral methyl group and its position. The comparison between the present six series and their corresponding phenyl analogues IIIna,b,c, indicated that the 2-naphthyl analogues, Ina,b,c, exhibit the highest mesophase stability. Whereas, the steric effect of the protruded naphthalene group destabilises all mesophases and appear only monotropically. The results were discussed in terms of polarisability effect.

New non-symmetrical homologues series of Schiff base/ester series, 4-alkoxyphenylimino-4ʹ-phenyl-4ʹ’-alkoxybenzoates, have two terminal alkoxy groups (Im/n), were synthesised and investigated for t...

In order to study the influence of lateral Br substitution on mesophase behaviour, five homologous series of 4-substituted phenylazo phenyl 4ʹ-(3ʺ-bromo-4ʺ-alkoxyphenylazo) benzoates (Ina–e) have b...

Four new groups of Schiff base ester liquid crystal compounds, 4-((4ʹ-substituted phenylimino) methyl)phenyl–4″-alkoxybenzoates, Ina–d, were prepared and investigated for their mesophase formation and stability. Each group constitutes four homologous series that differ from each other by the polar substituent X (CH3O, CH3, H, and Cl). 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 FT-IR, 1H NMR, mass spectroscopy, and elemental analysis. The mesomorphic properties were investigated by differential scanning calorimetry and polarised light microscopy. Comparative studies between the present series and previously investigated 4-(4-substituted phenylazo)phenyl 4″-alkoxybenzoates revealed that the phenylimino mesogenic core increases the mesophase stability rather than the azo analogues.

Several binary systems made from two laterally substituted azo/ester isomers, namely 2ʺ- (and 3ʺ-) methyl-4-substituted phenyl 4ʹ-(4ʺ-alkoxyphenylazo) benzoates, where the length of the terminal alkoxy group = 8 and 16 carbons, while the other terminal substituent, X, varies between CH3O, CH3, H, Br and CN groups, were investigated using differential scanning calorimetry (DSC) and phases identified by polarised light microscope (PLM). For the sake of comparison, two another binary systems made from 2ʺ- (or 3ʺ-) methyl-4-substituted phenyl 4ʹ-(4ʺ-alkoxyphenylazo) benzoates (n = 8 and X = CH3) each was mixed with its laterally neat analogue and similarly investigated. Results were discussed on the basis of constructed phase diagrams whereby various mesomorphic properties were observed dependent on X, n, and position of the lateral methyl group. In most of the cases, the mixtures exhibited eutectic compositions, while linear or nearly linear nematic and smectic A-composition temperature dependence we...

Two homologous series of 4-alkoxyphenylazo 4ʹ-(2ʺ- (and 3ʺ-) methyl-) 4ʹ-substituted benzoates (IIna–f and IIIna–f, six series each) were prepared and investigated. Within each series, the length of the terminal alkoxy group varies among 6, 8, 10 and 12 carbons, while the other terminal substituent, X, is a polar group that alternatively changes between the electron-donating CH3O, CH3, and the electron-withdrawing Br, NO2 and CN groups, in addition to the un-substituted analogue, X = H, aiming to investigate the effect of the different orientations of the methyl groups substituted on the central benzene ring, on the mesophase behaviour. The mesomorphic properties were discussed in terms of steric and polarisability effects. The mesophase stability was correlated with the polarisability anisotropy of bonds to the terminal substituent X. Comparative studies were made between the prepared isomers with each other and with the previously investigated laterally neat analogues 4-(4ʹ-alkoxyphenylazo) phen...

The thermal and mesophase behaviour of all possible 1:1 mixtures (In/Im) formed from any two homologues of 4-n-alkoxyphenylazo benzoic acids bearing different alkoxy chain lengths (n and m vary between 6 and 16 carbons), were investigated by differential scanning calorimetry (DSC) and phases identified by polarised light microscopy (PLM). Phase transitions were investigated as a function of the average alkoxy chain length (=(n + m)/2) of the mixed acids. A comparison, made between the present series and previously investigated simpler analogues, 4-n-alkoxy benzoic acids, revealed that increasing the length of the mesogenic core increased the stabilities of both the smectic C and nematic phases.

Four new groups of the di-fluoro-substituted 4-(2′-(or 3′)-fluoro phenylazo)-2-(or 3-) fluoro phenyl-4″-alkoxyphenylazo benzoates (In–IVn) were prepared and investigated for their mesophase behaviour. An alkoxy group of variable chain length (n = 6, 10 and 14 carbons) is attached to the terminal phenylazo benzoate moiety, and two lateral fluoro substituents are attached individually with different orientations to the other two adjacent rings. The molecular structures of the prepared compounds were confirmed by Fourier transform infrared spectroscopy and 1H NMR spectroscopy. The study aims to investigate the steric effect of the spatial orientation and relative positions of the two lateral fluorine atoms on the mesomorphic properties in their pure states. The mesophase behaviour was investigated via differential scanning calorimetry and mesophases were identified by polarised light microscopy. The investigation shows that these compounds exhibit high enantiotropic mesophases (SmC and N) and broad mesophase...

In order to investigate the effect of lateral methyl substitution on the mesophase behaviour of the previously investigated laterally neat 4-substituted phenyl 4ʹ-(4ʺ-alkoxyphenylazo) benzoates (Ina–e), five homologous series of 4-substituted phenyl 4ʹ-(3ʺ-methyl-4ʺ-alkoxyphenylazo) benzoates (IIna–e) were prepared in which, within each homologous series, the length of the terminal alkoxy group varies between 8, 10, 12, 14, and 16 carbons, while the other terminal substituent, X, is a polar group that alternatively changed between the electron-donating CH3O and CH3 groups, and the electron-withdrawing Br and CN groups, in addition to the unsubstituted analogue. Two other isomeric series (IIIna–e) were also prepared in which the methyl group is laterally attached, this time, to position 2 of the same ring, aiming to investigate the effect of the different orientation of the methyl groups on the mesophase behaviour of the produced isomers. The results were discussed in terms of steric, mesomeric, and polari...

A series of 4-alkoxyphenylazo-4′-phenyl-4′′-alkoxybenzoates bearing two terminal alkoxy groups (I m + n), where m and n denote the number of carbon atoms in the alkoxy groups attached to the phenylazo and benzoate moieties, respectively, was synthesised, and the molecular structures were established via elemental analyses, IR, NMR and mass spectroscopy. First, the thermal transitions and mesophase characteristics of any two isomeric molecules, having the same molecular length but with differently proportionated alkoxy groups, were investigated by differential scanning calorimetry and polarised-light microscopy. All compounds investigated proved to have a wide smectic C and nematic liquid crystalline ranges, except for the lower homologous (I 6 + 8 and I 8 + 6) where they are purely nematogenic. Mesophases were confirmed by the miscibility method, using dodecyloxybenzoic acid as the mesophase reference. Second, the mesophase behaviours of binary mixtures of isomeric compounds, bearing the same total alkoxy...

Twentyfour liquid crystalline esters of the type 4-(n-C n H2n+1O)C6H4COOC6H4OOCC6H4-X-4 have been investigated for their phase behaviour. These compounds constitute six homologous series that differ from each other by the substituent X. The latter varies between CH3O, CH3, Cl, CN, NO2, and n-C n H2n+1O, and the number (n) of carbons varies, within a homologous series, between 6, 8, 14, and 16. All possible binary mixtures made from any two homologues were prepared and characterized for their mesophase behaviour by differential scanning calorimetry and polarizing optical microscopy.

Binary mixtures formed from components of the four series of unsymmetrical 1,4-phenylene bis-4-substituted benzoates, in which one substituent is a terminal alkoxy group with a number of carbon atoms kept constant (at n + 6, 8, 14 and 16) while the other substituent (X) ranges through CH3O, CH3, Cl, CN and NO2, were prepared and characterized for their mesophase behaviour. Transition temperatures of the mixtures prepared were measured by differential scanning calorimetry and identified by polarizing optical microscopy. Phase diagrams for the various binary combinations were constructed to investigate the dependence of the phase behaviour of mixed systems upon the electronic nature of the terminal group X, as well as on the chain length of the alkoxy group. The results are discussed in terms of mesomeric and polarizability effects.

The apparent solution dipole moments of compounds based on 4,4-di-substituted phenyl benzoate (ROC6H4COOC6H4X), I, where X is a cyano group and R a terminal linear alkyl chain ranging from C12 to C20, were determined in cyclohexane at 30 C. The compounds were also thermally characterized by polarized light microscopy and differential scanning calorimetry. Phase diagrams were constructed for various binary mixtures prepared from any two homologues of series I as well as for every one of them with the nitro analogue II, where X is a nitro group and R C16H33. The study was undertaken in order to investigate the effect of the alkyl chain length on the mesophase behaviour. In order to assess the influence of structural variation in the central mesogenic group on the mesophase stability of pure and mixed compounds, the investigation was extended to cover binary mixtures of any two of the three compounds: analogue II (X=OC16H33), and the symmetric dialkoxy substituted phenyl esters (C16H33OC6H4COO)2 A, where A i...

Two binary mixtures, prepared from either 4-cyanophenyl 4-hexadecyloxybenzoate (Ib) or 4-nitrophenyl 4-hexadecyloxybenzoate (Ic), with 4-carboxyphenyl 4-hexadecyloxybenzoate (Ia), were thermally characterized to construct the phase diagrams for the two systems Ia/Ib and Ia/Ic. Due to differences in the smectic layering between the individual components of each system, phase separation took place either in the solid or in the mesophase. A mathematical relation was derived to calculate the composition of each phase in the solid state. Another two phase diagrams were constructed for binary mixtures of the linear dimer molecule, 4-hexadecyloxybenzoic acid (III) with either the acid Ia or its isomeric derivative, 4-hexadecyloxyphenyl 4-carboxybenzoate (II).

4-Substituted phenyl-4-hexadecyloxybenzoates and 4-hexadecyloxyphenyl-4-substituted benzoates were prepared and thermally characterized by differential scanning calorimetry. Transition temperatures were identified by polarized-light microscopy. Substituents were chosen to cover a wide range of electronic and dipolar characteristics. Binary mixtures of different components were prepared and similarly characterized to construct their phase diagrams. In mixtures of the 4-CN and 4-NO2 analogues, enhanced SmA mesophases were found when either of these esters was mixed with one of the methoxy analogues. A weak molecular complex is proposed to account for this non-ideal solution behaviour. Linear or slightly enhanced mixture behaviours were found for the nitro or cyano derivatives when mixed with each other. The results are interpreted in terms of electronic, dipolar, and molecular interactions.

Transition temperatures of binary mixtures of the two series, 4-hexadecyloxyphenyl-4- substituted benzoates (Ia-d) and 4-substituted phenyl-4-hexadecyloxybenzoates (IIa-d), have been determined on cooling and the phase diagrams compared with those previously obtained on heating. Tc values for the monotropes and the non-LC analogues have been evaluated by extrapolation. Examination of both series revealed that the square root of Tc is related to the polarizability anisotropy, Delta alphaX, of the CAr-X bond, except for the methoxy derivatives.

4-Hexadecyloxyphenyl-4-substituted benzoates, Ia-d, and 4-substituted phenyl-4- hexadecyloxy benzoates, IIa-d, with the substituents CH3O, Cl, CN, and NO2, respectively, were prepared and characterized by infrared spectroscopy and the apparent solution dipole moment measured using cyclohexane as a solvent. Smectic A mesophase stability was investigated by differential scanning calorimetry and polarized light microscopy. The effects of structural changes on phase transitions in these two series of compounds are discussed in terms of dipole and mesomeric effects.