Synthesis and Some Properties of Low Melting Ferroelectric Liquid Crystals of Benzylidene Anilines

A series of chiral benzylidene-aniline compounds, 4-alkoxybenzylidene 4′-(2-methylbutyloxycarbonyl)anilines, have been synthesized and their mesomorphic properties are examined. They showed a monotropic chiral smectic C phase in conjunction with enantiotropic smectic A phase, and their chiral smectic C—smectic A phase transition temperatures are around room temperatures. Their spontaneous polarization values are moderately higher than those of DOBAMBC “4-decyloxybenzylidene 4′-amino-(2-methylbutyl)cinnamate”.     

Chain Ordering and Sm-N Transition in Different Members of the Homologous Series 4-(4′- n-AIkoxy Benzylideneamino) Biphenyls

Our extension of Marcelja's theory of nematic-isotropic transition to the smectic A phase is used to calculate the smectic A-nematic (Sm-N) transition temperatures for the homologous series 4–(4′- n-alkoxy benzylideneamino) biphenyls. In a mean field calculation, explicit inclusion of the conformational energies of the alkyl chain of a molecule in the partition function shows an even-odd effect generally observed in experiments on Sm-N transitions. It is found that the members of this series showing the smectic phase will have first order Sm-N transitions and the transition entropies for individual members are calculated.     

Mesomorphism dependence on terminal end groups

A novel homologous series of liquid crystals (LC) 4-(4′-n-alkoxy cinnamoyloxy)-4′′-bromobenzylbenzoate was synthesized and studied with a view to understanding and establishing the relation between LC properties and the molecular structure. The novel series comprises 11 members, and all the members exhibit mesomorphism as enantiotropic smectic. None of the homologues are nematogenic, even in the monotropic condition. Transition temperatures were determined by an optical polarizing microscope equipped with a heating stage. The textures of smectic phase are of the type A or C. The transition curves Sm-I and Cr-Sm behave in a normal manner in the phase diagram. An odd-even effect is exhibited by the Sm-I transition curve. Thermal stability for smectic is 102.6°C. Mesomorphism commences from the very first member of the series. The series is entirely smectogenic and of middle-order melting type whose mesomorphic phase length ranges from 7.4°C to 60.9°. Analytical and spectral data confirmed the molecular structures of homologues. The mesomorphic properties of the present series are compared with structurally similar homologous series.     

Novel Cinnamate Esters—Synthesis and Mesomorphic Properties in Relation to Molecular Structure

A novel homologous series 4-[4′-n-alkoxy cinnamoyloxy] benzyl cinnamates consisting of 11 homologs was synthesized and studied with a view to understanding and establishing the relation between molecular structure and mesomorphic behavior of a substance. Mesomorphic behavior of the series commences from the third homolog and then continues until the last hexadecyloxy homolog. The first and second members of a series are non-mesomorphic. Nematogenic mesophase formation is observed from the propoxy homolog to the hexadecyloxy homolog, but the smectogenic mesophase formation is observed from the hexyloxy homolog to the tetradecyloxy homolog. All mesomorphic transitions are enantiotropic in nature. Transition temperatures were determined by an optical polarizing microscopy equipped with a heating stage. The textures of the nematic mesophase are threaded or Schlieren in type and that of the smectic mesophases are focal conic fan shaped of the smectic A or smectic C type. A phase diagram of the series shows a normal behavior of the transition curves with a minor abnormality of the last three homologs for the nematic-isotropic transition curve. The average thermal stability for smectic and nematic mesophases is 176.0°C and 219.3°C, respectively. Analytical and spectral data agree with the molecular structures of homologs. Mesomorphic phase length varies between 22°C and 76°C. Smectic phase length varies from 6°C to 33°C and nematic phase length varies from 22°C to 54°C. Thus, the novel present series is predominantly nematogenic and partly smectogenic. Mesomorphic properties of the novel series are compared with structurally similar other known homologous series.     

The Synthesis of Fluorine Containing Phenyl Benzoates and Their Properties as Liquid Crystals

A new series of fluorine containing phenyl benzoates has been synthesized and the transition temperatures of these compounds have been determined. A series of 4-trifluoromethylphe 4nyl 4-n-alkybenzoates showed no liquid crystalline behaviour, but the 4-trifluoromethylphenyl 4-n-alkoxybenzoates series, with six carbons or more in alkoxy chain, was mesomorphic. The 4-cyanophenyl 4-perfluoroalkylbenzoates showed smectic liquid crystalline properties.     

The Smectic A-Smectic A Transition in a Homologous Series of 4-(4-Alkoxyphenoxycarbonyl)phenyl 5-Cyano-2-furancarboxylates

The thermal properties for a homologous series of 4-(4-alkoxyphenoxycarbonyl)phenyl 5-cyano-2-furancarboxylates have been examined. The smectic A phase commences from the hexyloxy homolog, and the octyloxy, nonyloxy and decyloxy homologs show two kinds of smectic A phases and experience the S_A-S_A transition. The lower phase which shows a typical fan shaped texture is assigned to a smectic A with a bilayer arrangement of the molecules (S_A2). The higher phase which shows a typical fan shaped texture on the cooling stage and a broken fan one on the heating stage, is assigned to a smectic A with a partially bilayer arrangement of the molecules (S_Ad). The S_A-S_A transitions could be easily detected by both differential scanning calorimeter and optical microscopic method.     

Mesomorphic Properties of Di- (4 - Alkoxyphenyl) and Di- (4 - Alkanoyloxyphenyl) Tetrathiafulvalenes

The polymorphism of the di- (4 - alkoxyphenyl) and di- (4 - alkanoyloxyphenyl) tetrathiafulvalenes (TTF) is investigated. In the dialkoxy series, the short chain derivative exhibits a smectic G phase and a nematic phase. The latter phase disappears in the long chain derivative. The dialkanoyloxy derivatives exhibit a smectic G phase (for short chains) and a smectic C phase (for long chains). A plot of the mesormorphic-isotropic transition temperatures against the number of carbon atoms of the substituent shows the usual odd-even effect. Some tetra (alkoxyphenyl) tetrathiafulvalenes are described, unfortunately they have no mesomorphic properties.     

The Existence of SA 1, SA d,SA 2 and S∼C Smectic Phases in the New Series 4-Alkoxyphenyl-4′- [4″-Cyanobenzyloxv] Benzoates

A homologous series of 4 - alkoxyphenyl-4′-[4″-cyano-benzyloxy] benzoates have been synthesized. Within this series three smectic A phases : S_{A 1}, S_{A d} and S_{A 2} were identified by mean of small angle X-Ray scattering. Furthermore three derivatives exhibit the novel smectic phase made of ribbons S～_C.     

Investigation of the Homologous Series of 4-Propionyl–4′-n-Alkanoyloxyazobenzenes by X-Ray Diffraction

A study of the homologous series of liquid cristalline 4-propionyl-4′-n-alkanoyloxyazobenzenes was performed by x-ray diffraction. Two indipendent parame ters were used, namely the temperature and the paraffinic chain length, in order to obtain some structural in formation. In particular the molecular layer thickness was obtained as a function of the temperature for the different phases and different homologous. A linear de pendence of the molecular layer thickness as a function of chain length was found for the crystalline phase as it was previously observed for the smectic A phase. By comparison of the present data with those of the series 4-acetyl-4′-n-alkanoyloxyazobenzenes, a bilayer molecular organization similar to that of the smectic A phase appears as very probable also for the crystalline phase.     

Mesomorphism dependence on lateral substitution and central bridge

A novel ester homologous series was synthesized and studied with a view to understanding and establishing the effects of molecular structure on liquid crystal properties with a common laterally substituted –OCH3 group and changing terminal groups. The novel series consists of twelve members. The C₁ to C₃ members are not liquid crystals and the rest of the members C₄ to C₁₆ are smectogenic without exhibition of nematic character. Textures of smectic phase are focal conic fan shaped of the type A or C. The transition temperatures and textures of smectic mesophases were observed through hot stage polarizing microscopy (POM). The transition curves (Cr-I or Cr-M and Sm-I) behaved in normal manner. Analytical and spectral data support the molecular structures. Average thermal stability for smectic is 77.25°C and smectogenic mesophase ranges from 15°C to 33°C. Liquid crystal properties of the present series are compared with structurally similar homologous series. Thus, the series is smectogenic only with three homologs nonmesogenic.     

Synthesis and Mesomorphic Phase Behavior of Laterally Substituted Novel Azoesters

A novel homologous series of 4(4′-n-alkoxy benzoyloxy)phenylazo 2′′-chloro-3′′-methyl benzenes was synthesized and studied for mesophase behavior dependence on molecular structure. The nematogenic mesophase is exhibited from the first to the last member and the smectogenic mesophase from the hexyloxy to the tetradecyloxy member of the series. The nematic mesophase is of a threaded or Schlieren type, and the smectic mesophase is of a focal conic fan of the type A or C. Mesomorphic properties of the present novel homologous series are compared with other structurally similar homologous series.     

Dependence of liquid crystallinity on molecular rigidity

A novel homologous series of liquid crystals (LC) of chalconyl derivatives is synthesized and studied with a view to understanding and establishing the effects of molecular structure on liquid crystal properties. The novel series consists of 12 homologues. Nematogenic LC property commences from C₃ and continues up to C₁₄ and the smectogenic mesophase is exhibited from C₄ to C₁₆. The C₃ homologue is a monotropic nematic and the rest of the homologues are enantiotropically smectic and nematic or only smectic (C₁₆). Transition curves Cr-Sm, Sm-N, Cr-I, and N-I behave in normal manner with exhibition of odd-even effect, showing phase behaviors of the series.     

Mesomorphism dependence on molecular rigidity with reference to ‒CH˭CH‒ unit of central bridge

A novel ester homologous series of rich mesomorphism and low temperatures with unexpected phase behaviors of eleven homologues was synthesized and studied with a view to understanding and establishing the relation between mesomorphic behaviour and the molecular structure of a series 4-(4′-n-alkoxybenzoyloxy)-4″-chlorobenzyl cinnamates. All the members of the novel series are enantiotropically smectogenic and the octyloxy (C₈) to hexadecyloxy (C₁₆) homologues are enantiotropically nematogenic, in addition to smectogenic. Odd–even effect is observed for Sm?I/Sm?N transition curve but it is absent for N?I transition curve. Textures of nematic phase are threaded or Schlieren and that of the smectic phase are fan shaped or batonates of smectic-A type phase or Smectic-C type for C₁₆ homologues as judged directly from a heating stage of an optical polarizing microscopy. Analytical and spectral data confirmed the molecular structures of novel homologues. Mesomorphic properties of present series are compared with the structurally similar other known series. The average smectic and nematic thermal stabilities are 92.78°C and 100.8°C, respectively. Mesophase length minimum to maximum for smectic and nematic are 21.0°C to 31.1°C and 8.4°C to 42.6°C respectively. Thus, the present novel series is partly nematogenic and fully smectogenic with considerable degree of mesomorphism and low melting type.     

Mesomorphism Dependence on the Position of Substitution of a Pair of Esters

A novel homologous series of ethylene derivatives of thermotropic liquid crystals has been synthesized. The methoxy to octyloxy derivatives are nematogenic, the decyloxy to tetradecyloxy derivatives are smectogenic, in addition to nematogenic, and the hexadecyloxy homologue is smectogenic only. All the members of the series are enantiotropically mesogenic. Thermotropic behavior was determined by an optical polarizing microscope equipped with a heating stage and Differential Scanning Calorimetry (DSC) study. Analytical and spectral data confirm the molecular structures of homologues (infrared, nuclear magnetic resonance, mass spectra, X-ray, and DSC data). Textures of the nematic phase are threaded or Schlieren and that of smectic phase are focal conic fan-shaped of smectic A or C. Transition curves of the phase diagram behave in a normal manner except one or two deviations from the normal trend. The mesophase range (Sm+N) varies from 3°C to 44°C. The average thermal stability for smectic is 93°C and that for nematic 117.4°C. The LC behavior of the novel series is compared with a structurally similar known series.     

Phase Diagrams of New Compounds with Nematic Reentrant Mesophases

Two new series of compounds exhibiting nematic and smectic reentrant mesophases are presented here; the first one is 4-n-alkoxy benzoyloxybenzylidene 4'-cyanoaniline series the second one the 1-(4-n-alkylbenzoyloxyphenyl) 2-(4'-cyanophenyl) ethane series. Isobaric binary phase diagrams are plotted for each compound by means of the contact method and the mesophases so identified.     

Study of the Effect of Lateral Substitution on Mesogenic Behavior with Reference to -CH=CH- Unit

A novel cinnamate ester homologous series has been synthesized and studied with a view to understanding and establishing the effects of molecular structure on liquid crystal (LC) properties with a focus on the highly polar methoxy group as a lateral substituent. The series consists of twelve homologs; of which C₁–C₅ are nonmesogenic, and the rest of the homologs are enantiotropically smectogenic or and nematogenic. The texture of nematic phases is threaded or Schlieren and that of the smectic is either smectic A or C, as recognized and determined through an optical polarizing microscope equipped with a heating stage. The Sm-N I and N-I transition curves exhibit odd-even effects and behave in normal manner. The Cr-I M behaves in normal manner. Analytical and spectral data confirm the molecular structures of homologs. The average thermal stabilities for smectic and nematic are 125.3 C and 129.8 C, respectively, whose total mesophase length varies from 13 C to 51 C. Some LC properties of present series are compared with the structurally similar known series.     

Synthesis of 1 - (4-Alkoxy or Alkyl- Benzoyloxy-Phenyl) - 2- (4′- Pentylphenyl) - Ethanes. Influence of the Central Group on the Mesomorphic Properties

An homologous series of mesomorphic compounds, the I-(4-alkoxy or alkyl-benzoyloxyphényl)-2-(4′-pentylphenyl)-ethanes, has been synthesized. The compounds with R = alkyl have low-melting points and wide mesomorphic ranges, for example from 33.5°C to 106.5C. The compounds with R = alkoxy exhibit a smectic polymorphism; for example a compound of this series is successively smectic B, F and C. The influence of the central linkage when the ethane group is replaced by an ester, single bond, ethylene, azomethine, azo, methylenecetone or cetone groups, is discussed.     

Synthesis and Mesomorphic Characterisation of Chiral Homologues

Abstract

Chiral liquid crystals have attracted considerable interest as they exhibit a good variety of modulated phases. We have synthesised a homologous series viz., 4-(4^!-n-alkoxy benzoyloxy) benzylidene-4^!!?1-(s)-methyl propoxy anilines, incorporating a terminal chiral centre, inorder to obtain better understanding of the relationship between molecular structure and appearance of SmC* phase in the molecules. It is observed that, in the present series the lower members upto butyl are pure nematogens, while pentyl to hexadecyl derivatives exhibit classical smectic as well as nematic mesophases. An additional smectic C* phase is observed in the middle octyl to dodecyl homologues. The homologues have been characterised by IR, NMR and DSC. Their mesomorphic properties have been compared with structurally related homologous series.     

Mesomorphism dependence on central bridge (-COO-CH2-) and terminal end group (-Br)

A novel series of liquid crystalline (LC) ester materials has been synthesized and studied with a view to understanding the effects of molecular structure on LC behavior. The homologous series of eleven members is entirely enantiotropically smectogenic without exhibition of a nematic phase. Transition temperatures and the texture of smectic phase was determined by an optical polarizing microscope equipped with a heating stage (POM). Transition curves (Cr-Sm and Sm-I) showing phase behavior in a phase diagram behave in a normal manner. Textures of smectic phase are focal conic fan shaped of the type Smectic-A or Smectic-C. An odd–even effect is exhibited by the Sm-I transition curve. The average thermal stability for smectic is 91.2°C and the mesogenic phase length ranges between 3.6°C and 39.3°C. Thus, the novel smectogenic homologous series is a middle-ordered melting type whose LC phase is relatively middle ordered. The LC properties of the present series are compared with a structurally similar homologous series. Analytical and spectral data support the molecular structures.     

Novel Azoester Compounds with a Lateral Methyl Substituent

Twelve novel homologues with an azo linkage of the series 4-carbethoxy-[3′methyl-4′ (4^″-n-alkoxy benzoyloxy)] azobenzenes have been synthesized. The methyl to n-hexyl homologues exhibit only nematic mesophases, while the n-heptyl to n-tetradecyl homologues exhibit both smectic and nematic mesophases. The n-hexadecyl homologue exhibits only a smectic mesophase. The plot of transition temperatures versus number of carbon atoms in alkoxy chain exhibits an odd-even effect for the nematic-isotropic transitions. The mesogenic behavior of present series is explained by comparing each homolog of the related mesogenic series. The synthesized compounds were characterized by a combination of elemental analysis and standard spectroscopic methods. For the exhibition of mesomorphic property the role of ester and azo linkages has been discussed. The impact of the lateral methyl group on mesomorphism is also discussed.