Synthesis,characterisation and liquid crystalline properties of some Schiff base and cinnamate central linkages involving 1,3,5-trisubstituted pyrazolone ring system and their Cu(II) complexes

Two new mesogenic homologous series, each containing 1,3,5-trisubstituted pyrazolone derivatives, 4-n-alkoxyphenyl and Schiff base–cinnamate central linkages, have been synthesised to give 4-[(5-hydroxy-3-methyl-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl) methyleneamino] phenyl 3-(4-n-alkoxyphenyl)acrylate [Series-A] and 4-[(5-hydroxy-3-methyl-1-p-tolyl-4,5-dihydro-1H-pyrazol-4-yl)methyleneamino] phenyl 3-(4-n-alkoxyphenyl)acrylate [Series-B] and their Cu(II) complexes have also been synthesised. These compounds were characterised by elemental analysis, Fourier transform infrared (FT-IR), proton nuclear magnetic resonance (¹H NMR), carbon-13 NMR (¹³C NMR) and ultraviolet (UV)-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 an enantiotropic nematic mesophase except propyl derivative, while a smectic A (SmA) mesophase is observed from the heptyl derivative and persists up to the last member of the homologous series. n-Heptyloxy derivative is monotropic for SmA phase. Series-B compounds also exhibit the enantiotropic nematic mesophase, while the SmA mesophase is observed from the heptyl derivative and persists up to the last member of the homologous series. n-Dodecyloxy derivative exhibits monotropic SmA and nematic mesophases. The mesomorphic properties of both series are compared with each other and the other structurally related compounds. The study reveals that cinnamate linkage containing liquid crystals have higher thermal stability compared to structurally related series containing chalcone linkage. In case of complex series, only one compound from each series gives nematic mesophase.     

Mesomorphic behavior of new azomethine liquid crystals having terminal iodo group

A series of azomethine esters,3-hydroxy-4-{[（4-iodophenyl）imino]methyl}phenyl alkanoates possessing even number of carbon atoms at the terminal alkanoyloxy chain(C_n-1H_2n-1COO-,n = 4,6,8,10,12,14) was synthesized.n-Butanoyloxy was found non-mesogenic,whilst n-hexanoyloxy to n-tetradecanoyloxy exhibited enantiotropic smectic A phase with fan-shaped texture.It was found that the length of terminal alkanoyloxy chain influenced the mesomorphic properties.     

Azomesogens containing an ethoxyethyl terminal chain: synthesis and characterization

Two homologous mesogenic series, the ethoxyethyl 4-(4'-n-alkoxyphenylazo)benzoates (I) and the ethoxyethyl [4-(4'-n-alkoxybenzoyloxy)phenylazo]-4'-benzoates (II), both containing a terminal ethoxyethyl chain, have been synthesized. In series I, all nine members synthesized exhibit only an enantiotropic smectic A mesophase. In series II, all 12 homologues exhibit an enantiotropic nematic mesophase; a smectic A phase appears in the n-butyloxy derivative as a enantiotropic phase and persists through to the n-hexadecyloxy member. 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 the ethoxyethyl chain on mesomorphism.     

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.     

Mesogenic cinnamates with a substituted ethyl terminal chain

Two new mesogenic homologous series of liquid crystalline cinnamates with substituted ethyl tails, β-methoxyethyl [4-(4'-n-alkoxycinnamoyloxy)benzoates (I) and β-chloroethyl [4-(4'-n-alkoxycinnamoyloxy)benzoates (II), have been synthesized and characterized by a combination of elemental analysis and standard spectroscopic methods. In series I, lower-chain members exhibit nematic mesophase, middle members exhibit enantiotropic nematic as well as smectic A (SmA) mesophases, whereas higher members exhibit only an enantiotropic SmA mesophase. In series II, methoxy to n-butyloxy derivatives exhibit a monotropic nematic mesophase. The SmA mesophase commences from n-propyloxy derivative as monotropic and persists up to the last member synthesized. The mesomorphic properties of present series were compared with each other and with a structurally related mesogenic homologous series to evaluate the effects of substituted ethyl tail and cinnamoyloxy central linkage on mesomorphism.     

Azomesogens with methoxyethyl tail: Synthesis and characterization

Two new mesogenic homologous series are synthesized from methoxyethyl 4-(4′-hydroxyphenylazo) benzoate. In series I the phenolic -OH group is alkylated, whereas in series II it is esterified with 4-n-alkoxybenzoyl group. In series I, all the nine members synthesized exhibit only enantiotropic smectic A mesophase. In series II, all the twelve homologues exhibit enantiotropic nematic mesophase. Smectic A mesophase appears from then-decyloxy derivative as a enantiotropic phase and persists till the last n-hexadecyloxy member. The mesomorphic properties of both the series are compared with each other and also with the properties of other structurally related series to evaluate the effect of the methoxyethyl tail on mesomorphism.     

Synthesis and mesomorphic properties of naphth-2-yl 2-pyridylmethyl ketones and their copper (II) complexes

The synthesis, characterization and mesomorphic properties of a homologous series of 6-alkoxy naphth-2-yl 2-pyridylmethyl ketones and their copper(II) complexes are reported. All the ligands and their copper complexes, with exception of the lowest homologues, exhibit enantiotropic mesophases. According to textural observations, the ligands display nematic and smectic transitions depending on the length of the alkoxy chain on the pyridine moiety, while the mesogenic complexes show exclusively smectic transitions. In comparison with the phenyl analogues, stabilization of the mesophase and a greater tendency to smectic ordering through incorporation of the naphthyl group into the molecules is confirmed.     

Synthesis and mesomorphic properties of some platinum(II) and oxovanadium(IV) complexes

The synthesis and mesomorphic properties of a homologous series of N-(2-hydroxy-4-n-alkoxybenzylidene)-4'-n-decylphenylanilines and their platinum(II) and oxovanadium(IV) complexes are reported. All the ligands and their metal chelates exhibit enantiotropic mesophases, predominantly smectic A and smectic C phases. The transition temperatures and enthalpies have been determined for most of the compounds. The platinum(II) complexes have higher melting points and mesophase thermal stabilities. However, the oxovanadium(IV) complexes have a wider thermal range for the mesophase. Both platinum(II) and oxovanadium(IV) complexes containing only a chain on the biphenyl moiety exhibit a nematic phase.     

Synthesis and Mesomorphic Properties of Novel γ-Substituted β-Diketonates

The synthesis and mesomorphic properties of two series of novel γ-substituted β-diketonates have been reported. All of the compounds 2,4-dioxo-3-pentyl 4-[[4-(n-alkoxyl) cinnamoyl]oxy]cinnamatetes Ia-If (n=7-12) exhibit two monotropic phases(N and Sc) and have a wider mesophase range than the compounds 2,4-dioxo-3-pentyl 4-[[4-(n-alkoxyl) benzoyl]oxy] cinnamatetes Ⅱa-Ⅱf (n=7-12), which display one monotropic nematic phase (n=7-10) or an enantiotropic nematic phase for n=11 or two enantiotropic phases (N and Sc)for n=12.     

Synthesis of two naphthyl-containing homologous series of mesogenic ligands and the related metallomesogens containing Cu(II)

Two new naphthyl-containing homologous series of mesogenic ligands, the 4-n-alkoxy-2-hydroxybenzylidene-2'-naphthylamines (series I) and 4(4'-n-alkoxybenzoyloxy)-2-hydroxybenzylidene-2'-naphthylamines (series II), as well as the related metallomesogens of higher homologues containing a Cu(II) atom, have been synthesized. All the ligands and complexes were characterized by a combination of elemental analysis and standard spectroscopic methods. In series I, n-heptyloxy and n-octyloxy derivatives are non-mesogenic whereas the remaining higher members synthesized exhibit a monotropic nematic mesophase. In series II, all the members synthesized exhibit an enantiotropic nematic mesophase. All the metallomesogens of series I synthesized exhibit a monotropic smectic A mesophase, except for the n-octyloxy derivative, which is non-mesogenic, whereas metallomesogens of series II exhibit enantiotropic nematic mesophases up to the n-tetradecyloxy derivatives; the n-tetradecyloxy and n-hexadecyloxy derivatives also exhibit smectic C mesophases. All the members of series II and their metallomesogens exhibit mesophases with wide temperature ranges and greater thermal stability as compared to series I and their metallomesogens, respectively. The mesomorphic properties of both the present series and their metallomesogens are compared with each other and with other structurally related series to evaluate the effect of the naphthalene moiety on mesomorphism.     

Mesogenic cinnamates with a substituted ethyl terminal chain*

Two new mesogenic homologous series of liquid crystalline cinnamates with substituted ethyl tails, β‐methoxyethyl [4‐(4′‐n‐alkoxycinnamoyloxy)benzoates (I) and β‐chloroethyl [4‐(4′‐n‐alkoxycinnamoyloxy)benzoates (II), have been synthesized and characterized by a combination of elemental analysis and standard spectroscopic methods. In series I, lower‐chain members exhibit nematic mesophase, middle members exhibit enantiotropic nematic as well as smectic A (SmA) mesophases, whereas higher members exhibit only an enantiotropic SmA mesophase. In series II, methoxy to n‐butyloxy derivatives exhibit a monotropic nematic mesophase. The SmA mesophase commences from n‐propyloxy derivative as monotropic and persists up to the last member synthesized. The mesomorphic properties of present series were compared with each other and with a structurally related mesogenic homologous series to evaluate the effects of substituted ethyl tail and cinnamoyloxy central linkage on mesomorphism.     

Nematogenic and smectogenic liquid crystals from new heterocyclic isoflavone derivatives:Synthesis,characterization and X-ray diffraction studies

A new series of liquid crystals comprising eight heterocyclic isoflavone esters,7-alkanoyloxy-3-[4’-(3-methylbutyloxyphenyl)]- 4H-1-benzopyran-4-ones exhibiting enantiotropic nematic(N) and smectic C(SmC) phases were synthesized and investigated.The mesomorphic properties of all derivatives were investigated by means of differential calorimetry and polarized optical microscopy. Wide angle X-ray diffraction technique was employed to investigate the molecular packing associated with the intermolecular interaction as well as the correlation between the thermal behaviour of these compounds with their anisotropy properties within a mesophase.     

Liquid Crystalline Thiadiazole Derivatives: Thiadiazole Derivatives Containing Pyridine Ring as Terminal Group

The synthesis and mesomorphic behavior of a new series of liquid crystals containing 1, 3, 4‐thiadiazole and pyridine rings with ‐CH = N‐ central group are reported. All compounds exhibit enantiotropic smectic A mesophase, but the Schiff's base analogues have no mesomorphic behavior. The influence of the pyridine ring and thiadiazole ring is discussed.     

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.     

Azomesogens containing a β-chloroethyl terminal chain: synthesis and characterisation

In this paper, we present the synthesis and characterisation of two new mesogenic homologous series, β-chloroethyl 4-(4′-n-alkoxyphenylazo) benzoates (I) and the β-chloroethyl [4-(4′-n-alkoxybenzoyloxy)phenylazo]-4”-benzoates (II), containing a terminal β-chloro ethyl chain. Series I was synthesised by alkylation of β-chloroethyl 4-(4′-hydroxy phenylazo) benzoate with an appropriate alkyl halide, whereas series II was synthesised by esterification of β-chloroethyl 4-(4′-hydroxyphenylazo) benzoate with an appropriate 4-n-alkoxybenzoic acid. The molecular structures of these new compounds of both the series were characterised by combination of element analysis and a standard spectroscopic method. The mesomorphic behaviour was studied mainly by use of a polarised microscope and, in some cases, differential scanning calorimeter as well. In series I, all nine members synthesised exhibited only an enantiotropic smectic A mesophase. In series II, all 12 homologues exhibited an enantiotropic nematic mesophase; a smectic A phase appeared in the n-octyloxy derivative as an enantiotropic phase and persisted through to the n-hexadecyloxy member. The mesomorphic properties of both series were compared with each other and also with the properties of other structurally related series to evaluate the effects of the β-chloroethyl tail on mesomorphism.     

Synthesis and Liquid Crystalline Properties of 3-Substituted Pentane-2,4-dione, Pyrazole and Isoxazole Derivatives

The γ-substituted β-diketonate 2,4-dioxo-3-pentyl 4-[4-（n-octyloxy）cinnamoyl]oxybenzoate 1 and its pyrazole and isoxazole derivatives （2 and 3 respectively） have been synthesized and characterized by the spectroscopic methods and elemental analysis. The mesogenic properties of these compounds have been studied by polarizing optical microscopy （POM） and differential scanning calorimetry （DSC）. A monotropic nematic mesophase was observed for the β-diketonate 1, in contrast, the pyrazole 2 displays an enantiotropic smectic A and isoxazole 3 exhibits an enantiotropic nematic mesophase. The relationship between the structure and liquid crystalline properties has also been discussed.     

Synthesis and mesomorphic properties of 3-(4-n-alkyloxyarylaminomethylene)chroman-2,4-diones

The synthesis, characterisation and mesomorphic properties of new liquid crystals are reported. The goal was to obtain amides starting from 7-decanoyloxychromone-3-carboxylic acid and 4-n-alkoxyanilines. However, instead of the expected amides, in each case a mixture of two isomeric E/Z enaminones was isolated, with a ratio 3/1. The mesophase behaviour of the five mixtures was characterised and studied using differential scanning calorimetry and polarising optical microscopy. The transitions are enantiotropic, the peaks being sharp and the mesomorphic range wide. All the compounds exhibit a smectic C phase and the derivatives with shorter chains also exhibit a nematic phase.     

Phase transfer Pd(0)/Cu(I) catalysed polymerization reactions 7. Synthesis and thermotropic behaviour of 1,4-bis[2-(3',3'-difluoro-4',4'-di-n-alkyloxyphenyl)-ethynyl]benzene dimers

The symmetrically difluorinated aryl-acetylene dimers, 1,4-bis[2-(3',3'-difluoro-4',4'-di-n-alkyloxyphenyl)ethynyl]benzenes (n = 7-12), were prepared by a one pot phase transfer. Pd(0)/Cu(I) catalysed, three step coupling of 1,4-diiodobenzene with 2-methyl-3-butyn-2-ol and the appropriate 1-bromo-3-fluoro-(4-n-alkyloxy)benzene. All members of the series display enantiotropic nematic and smectic C phases as well as an additional smectic mesophase in the sequence C-S-S_C-N-I. The textures observed by polarized optical microscopy strongly support identification of the second smectic phase as a S_E mesophase. The S_C temperature window increases as the length of the n-alkyloxy substituent increases, whereas the stability of the nematic and S_E temperature windows decrease. In these fluorinated dimers, destabilization of mesomorphic behaviour by lateral fluorine substitution is compensated by stabilization due to the large length to breadth ratio of the mesogen, such that melting and crystallization are depressed more than isotropization when compared to the non-fluorinated dimers.     

Mesogenic benzothiazole derivatives with methoxy substituents

Two new mesogenic homologous series containing 6-methoxybenzothiazole ring at the terminus of the molecule, viz. 2-(4′-n-alkoxyphenylazo)-6-methoxybenzothiazoles and 2-[4′-(4″-n-alkoxy-benzoyloxy) phenylazo]-6-methoxybenzothiazoles were synthesized. In series I,n-butyloxy to n-tetradecyloxy derivatives exhibit nematic mesophase. Smectic A mesophase commences from then-dodecyl-oxy derivative as a monotropic phase and is retained up to the last member synthesized. All the members of series II exhibit enantiotropic nematic mesophase. The mesomorphic properties of the present series are compared with other structurally related series to evaluate the effect of the benzothiazole ring and the methoxy substituent on mesomorphism. This paper was presented at the 10th National Conference on Liquid Crystals held at Bangalore during 9–11 October 2003     

Molecular engineering of liquid crystal polymers by living polymerization. II. Living cationic polymerization of 11-[(4-cyano-4′-biphenyl) oxy] undecanyl vinyl ether and the mesomorphic behavior of the resulting polymers

The synthesis and living cationic polymerization of 11-[(4-cyano-4′-biphenyl)oxy]-undecanyl vinyl ether ( 6 – 11 ) are described. The mesomorphic phase behavior of poly( 6 – 11 ) with different degrees of polymerization was compared to that of 6 – 11 and of 11-[(4-cyano-4′-biphenyl) oxy] undecanyl ethyl ether ( 8 – 11 ) which is the model compound of the monomeric structural unit of poly( 6 – 11 ). 6 – 11 displays a monotropic S_A and a monotropic nematic mesophase while 8 – 11 an enantiotropic S_A mesophase. Poly( 6 – 11 ) with low degrees of polymerization exhibits an enantiotropic S_A mesophase. Poly( 6 – 8 ) with high degrees of polymerization displays an enantiotropic S_X (i. e., an unidentified smectic phase) and an enantiotropic S_C mesophase. These results demonstrate that the transformation of the nematic mesophase of the monomer into a smectic mesophase after polymerization, occurs at the level of monomeric structural unit.