Study of mesomorphism dependence on molecular flexibility of an azoester series containing a napthyl unit

A novel azoester homologous series of liquid crystalline (LC) compounds: RO?C₆H₄-COO?C₁₀H₆-N:N-C₆H₄?OC₄H₉(n) without lateral substitution has been synthesized and studied with a view to understanding and establishing the effects of molecular structure on thermotropic LC substances with reference to tailed-end group. The novel homologous series consists of 13 homologs (C₁ to C₁₈) whose nematogenic and smectogenic mesomorphism commences enantiotropically from C₆ and C₁₂ members of the series, respectively. The C₁₂–C₁₈ homologs are smectogenic and C₆–C₁₈ are nematogenic, of which C₁₂–C₁₈ homologs are smectogenic plus nematogenic. The C₁–C₅ homologs are nonmesogenic. Transition temperatures and the textures of the homologs were determined and identified by an optical polarizing microscope (POM) equipped with a heating stage. Textures of a nematic phase are threaded or Schlieren and that of the smectic phase are of the type A or C. Transition curves Cr-M/I, Sm-N and N-I of a phase diagram behaved in normal manner except N-I transition temperature of C₁₀ homolog which deviated by 9°C–10°C from normal behavior. N-I transition curve exhibited odd-even effect. Analytical, spectral, and thermal data confirms the molecular structures of homologs. Thermal stability for smectic and nematic are 115.5°C and 138.5°C, respectively whose corresponding mesophaselengths are varied from 10.0°C to 16.0°C and 13.0°C to 24.0°C, respectively. Group efficiency order for smectic and nematic are derived from comparative study of structurally similar analogous series; as smectic: ?OC₄H₉ (n) > ?CH₃ > ?H; Nematic: ?H > ?OC₄H₉ (n) > ?CH₃     

Mesomorphism dependence on halogenated chalconyl esters in terms of molecular flexibility/rigidity

Vinyl carboxy central group containing a novel chalconyl ester homologous series: RO.C₆H₄.CH ? CH.COO.C₆H₄.CH ? CH.CO.C₆H₄.I (para) have been synthesized and studied with a view to understand and establish the relation between thermotropic liquid crystalline (LC) behaviors and the molecular structure. Novel chalconyl ester homologous series consists of thirteen homologs (C₁–C₁₈). C₁–C₃ homologs are nonmesogenic, C₄ homolog is enantiotropic nematogenic and the rest of the homologs (C₅–C₁₈) are enantiotropically smectogenic plus nematogenic. Phase transition temperatures and textures of LC phase were determined by an optical polarizing microscopy (POM) equipped with a heating stage. Cr-M/I, Sm-N, N-I transition curves in a phase diagram behaved in normal manner. Sm-N and N-I transition curves exhibited odd-even effect from C₄–C₁₀ or nearby C₁₀ homolog. Textures of nematic phase are threaded or Schlieren and that of the smectic phase are of the type smectic A or C. Analytical and spectral data confirms the molecular structure of homologs. Thermal stabilities for smectic and nematic mesophases are 155.0 and 180.7, respectively, and their corresponding mesophaselengths are varied from minimum to maximum at 17.0°C–39.0°C as well as 15.0°C–30.0°C. Thus, it is middle ordered melting type series. The group efficiency orders derived on the basis of smectic and nematic thermal stabilities are as under: Sm: -C₆H₄.I > -C₆H₄.Cl > -C₄H₃S and N:- C₆H₄.I > -C₆H₄.Cl > -C₄H₃S from comparative study of structurally similar analogous series     

Calorimetric Study of Crystalline and Liquid-Crystalline Polymorphism in the Homologues of Terephthal-bis-n-alkylaniline

The phase sequences of the homologues with n (the number of carbon atoms in the terminal alkyl chains) from 2 to 8 are obtained. At low temperatures, i) several crystalline modifications are found in each of the members with n = 4, 5, and 6 and ii) the monotropic transitions between crystal and smectic phase are observed in almost all the members. At intermediate temperature, iii) between the smectic H and C phases, the smectic F phase is found in the homologues with n ≥ = 5 by morphological observation or by a rheological method. The constancy of the temperature of the S_H(or S_F) – S_c transition with respect to “and broadening of the temperature range of S_H with increasing n in the expense of nematic phase are worthy of note. The even-odd effect of the end chain length n is observed very distinctively on the crystal melting and clearing point. Proton NMR measurement reveals a large mobility in the terminal alkyl chains in the crystal of the member with n = 6.     

Liquid Crystalline Phases in 4-Acetyl-4′-n-Alkanoyloxy-Azobenzenes

Abstract

The preparation and melting behaviour of the homologous series of 4-acetyl-4′-n-alkanoylox-azobenzenes, CH₃-CO-C₆H₄-N?N-C₆H₄-O-CO-(CH₂) _n -CH₃, (with n ranging from zero to 16) is reported. The melting behaviour has been investigated by means of thermal microscopy and differential scanning calorimetry. The experimental results indicate for almost all the compounds the presence of solid state polymorphism and a type A smectic; for one compound a type B smectic phase is also present. Some homologs present, in addition, a nematic phase.     

Study of the molecular structure on liquid crystal properties with reference to thermotropic azoester derivatives

An azoester homologues series: RO?C₆H₄?COO?C₁₀H₆?N?N?C₆H₄?OC₅H₁₁ (para) as novel liquid crystalline (LC) materials has been synthesized and studied with a view to understanding and establishing the effects of molecular structure on LC properties with reference to laterally substituted phenyl ring and terminally substituted ?OR and ?OC₅H₁₁ (n) groups; including ?COO? and ?N?N? central bridges. Novel homologous series of thermotropic LC variety consists of thirteen homologues (C₁ to C₁₈). C₁ to C₃ derivatives are nonliquid crystal (NLC); C₄ is only nematogenic and C₅ to C₁₈ are smectogenic plus nematogenic. All the mesogenic homologues (C₄ to C₁₈) are enantiotropically nematogenic or/and smectogenic as confirmed by a polarizing optical microscopy (POM) equipped with a heating stage. Transition curves Cr-I/M, Sm?N, and N?I behaved in normal manner in a phase diagram. Odd-even effect is exhibited by Sm?N and N?I transition curves. Analytical, spectral and thermal data confirms the molecular structure of novel homologues. Novel azoester series is predominantly nematogenic and partly smectogenic whose mesogenic temperatures ranges minimum to maximum from 79.0°C to 162.0°C. Thermal stability for smectic and nematic are 128.2°C and 147.7 °C, respectively. Thus, it is a middle ordered melting type of novel series whose total mesophaselength ranges from 20.0°C to 56.0°C. Textures of nematic are threaded or schlieren and that of smectic are smectic A or C.     

Molecular structural flexibility dependence of mesomorphism through ortho-substituted bromo group

A novel series of liquid crystal (LC) materials of Schiff's bases viz. RO-C₆H₄?CH?CH?COO?C₆H₄?N?CH?C₆H₄?Br (ortho) is synthesized and studied with a views to understanding and establishing the effect of molecular structure on liquid crystal properties and to provide novel thermotropic LC material to the scientific and technological community of research interest. The novel series consists of thirteen members (C₁ to C₈, C₁₀, C₁₂, C₁₄, C₁₆ &; C₁₈). All the members of a series are enantiotropic liquid crystals. Smectic (C₁₀?C₁₈) and nematic (C₁?C₁₈) property commence from C₁₀ and C₁ homologue respectively. Transition temperatures and the textures of homologues were determined using a polarizing optical microscope (POM) equipped with a heating stage. Transition curves Cr-M, Sm-N and N-I of a phase diagram behaved in normal manner. Odd–even effect is absent for Sm-N transition curve, but it is present for N-I curve. Sm-N transition curve is extrapolated to C₈ and C₆ nonsmectogenic homologues to determine and predict their latent ability for exhibition of smectic property. Analytical and spectral data confirms the molecular structures of homologues. Thermal stabilities of smectic and nematic are 85.4°C and 130.1°C °C whose upper and lower total mesophase length vary from 58.0°C to 06.0°C at the C₁₀ and C₁ = C₅ = C₆ homologue, respectively. Textures of nematic phase are threaded or Schlieren and smectic phase are of type A or C. LC properties of present novel series are compared with structurally series known series. Thus, present novel series is predominantly nematogenic and partly smectogenic with middle ordered melting type and considerable total mesophase length range.     

Mesomorphism dependence of a terminal or lateral alkoxy group

A novel homologous series of thermotropic mesomorphs has been synthesized and studied with a view to understanding and establishing the effect of molecular structure on mesomorphic properties with reference to rigidity and flexibility of the homologues series: RO-C₆H₄-CH?CH-CO-C₆H₄-OC₁₈H₃₇(n). The novel homologous series comprises 13 novel homologues (C₁ to C₁₈), from which 11 homologues are enantiotropically mesogenic (C₃ to C₁₈). Smectogenic mesophase commences from C₇ homologue, and nematogenic mesophase is exhibited by C₃ to C₁₈ homologues in enantiotropic manner. Thus, C₇ to C₁₈ homologues are enantiotropically smectogenic plus nematogenic. Textures of smectic phase are of the type A or C, and that of nematic phase are threaded or Schlieren as confirmed through an optical polarizing microscope equipped with a heating stage. Transition curve of a phase diagram behaved in a normal manner except N-I transition curve, which shows minor deviating trend (C₁₂ to C₁₈) from expected normal behavior. An odd-even effect is exhibited by N-I and Sm-N transition curves. Analytical, spectral, and thermal data confirm the molecular structures of novel homologues. Thermal stabilities for smectic and nematic are 52.7°C and 66.6°C, respectively, whose total mesophase lengths range from 12.0°C to 28.0°C. Thus, novel series of chalcones is a low melting series whose mesogenic transition temperatures vary between 38.0 and 86.0°C.     

Dependence of thermotropic mesomorphism on lateral nitro group

A novel homologous series RO-C₆H₄-COO-C₆H₃-(NO₂)-CO-CH?CH-C₆H₄OC₁₈H₃₇(n) para of chalconyl ester derivatives have been synthesized and studied with view to understanding the effect of an ortho substituted nitro group on thermotropic liquid crystal (LC) behavior. The novel homologous series consists of thirteen homologues (C₁ to C₁₈). The C₁ to C₄ homologues are nonliquid crystal (NLC) and the rest of the homologues (C₅ to C₁₈) homologues are enantiotropically nematogenic without exhibition of a smectic phase even in the monotropic condition. Transition temperatures were determined by an optical polarizing microscope (POM) equipped with a heating stage. Texture of nematic phase are threaded or Schlieren. Analytical, thermal and spectral data supported molecular structure of homologues. Thermal stability for nematic is 147.1°C whose mesophase lengths vary between 16.0 and 32.0°C the C₇ and C₁₈ homologues, respectively, and their mesogenic exhibition range between 96.0 and 166.0°C. Thus, the present novel series is middle ordered melting type, Group efficiency order is derived from comparative study of structurally similar series. The transition curves of a phase diagram behaved in normal manner except C₁₀ and C₁₆ homologues. Odd-even effect is observed for N-I transition curve. Group efficiency order derived is: -OC₁₂H₂₅ (n) > -OC₁₈H₃₇ (n) > -OC₁₈H₃₇ (n).     

Ferroelectric Liquid Crystals with New Chiral Building Blocks

Esterification of 4-nitrocinnamoyl chloride by new chiral alcohols((d) and (1) 2-butanol; (d) 2-heptanol), followed by reduction of the nitro group by a new reagent(SnC1₂), gives new chiral 4-aminocinnamates.Condensation of these amines with 4-alkyloxybenzaldehydes or terephthaldehyde gives Schiff bases showing in some cases chiral smectic C phases. A comparative study of the mesomorphism of both these compounds and the compounds of the DOBAMBC family is made, in order to evaluate the effect of the chiral building block structure on the liquid crystalline properties.During this study, a new compound has been prepared, which exhibits the smectic O phase: ((d) 1-methylhexyl)terephthalidene Bis 4-aminocinna-mate.     

Synthesis of novel ester series and study of its mesomorphism dependence on terminal end group with lateral –OCH3 group

Novel liquid crystal (LC) materials of ester derivatives were synthesized and studied with a view to understanding and establishing the effects of molecular structure on LC properties. The novel molecules consist of two phenyl rings bonded through –COO– central group and a laterally substituted methoxy group with –OC_nH_2n+1 as well as –COOCH₃ terminal end groups, and yielded 12 homologous members of an ester series. The C₁ to C₃ members are nonmesomorphic, the C₄ to C₁₂ members are enantiotropic nematic only, and the C₁₄ to C₁₆ members are enantiotropically smectogenic in addition to nematogenic. Transition temperatures and the textures of LC state were observed through an optical polarizing microscope (POM) equipped with a heating stage. The textures of nematic phase are threaded or Schlieren, and that of smectic phase are focal conic of the type A or C. Transition curves of a phase diagram behave in normal manner with the exhibition of an odd-even effect (only N-I). Analytical and spectral data support the molecular structures of the novel ester derivatives. The LC properties of the present series are compared with structurally similar other known series. The average thermal stability of the series is 93°C for smectic and 120.88°C for nematic and the mesogenic phase length ranges between 2°C and 46°C.     

Molecular Arrangement in Mesophases of Some p-n-Alkoxybenzoic Acids

The properties of an even homologous series of alkoxy benzoic acids have been investigated in the crystalline and mesomorphic states by means of thermal microscopy, x-ray scattering and dilatometry.

Structural parameters such as inter-lamellar distance d, and the molar volume V_m were studied as a function of the number n of methylene units of the alcoxy radical.

In the crystalline state and the smectic C state the variation of d and of V_m with n is perfectly linear. The angle of tilt of the paraffinic chains α′ and of the aromatic stems φ was determined in the crystalline state. It was found that both moieties have the same magnitude of the tilt. In the smectic C state the value of α′ was found to be 25° as compared to 60.7° in the crystalline state indicating a “pulling up” of hydrocarbon tails when passing from the crystalline state to the smectic state. The passage from crystalline into the smectic state is also accompanied by a strong increase in V_m. Analysis of data indicates that this increase is entirely due to the aromatic part of the molecule while the aliphatic chains have the same V_m as in the crystalline state. It is concluded that while in the crystalline state the cohesion of the phase is insured to a large extent by dimerized, hydrogen bonded molecules, in the smectic C state the cohesion is insured by attraction between extended aliphatic chains. Evidence is also given for the formation of cybotactic groups in the nematic phase of octyloxy benzoic acid.     

Study of mesomorphism and laterally substituted nitro group

A novel thermotropically mesomorphic, meta-substituted nitro group of chalconyl ester series, RO-C₆H₄-COO-C₆H₃-(NO₂)-CO-CH=CH-C₆H₄OC₁₂H₂₅(n) (para) is synthesized and studied with an aim to establish the relation between molecular structure and the mesomorphism with reference to changing molecular flexibility in presence of nitro lateral group. Novel homologous series consist of thirteen homologs (C₁–C₁₈) whose mesomorphism commences from C₅ homolog as enantiotropic nematogenic with absence of smectic property, even in the monotropic condition. Transition temperatures of novel substances were determined by an optical polarizing microscope, equipped with a heating stage (POM). Textures of a nematic phase are threaded or Schlieren. N-I transition curve exhibited narrow, sharp and short odd-even effect; with deviating trend in a phase diagram. Analytical, spectral and thermal data confirmed the molecular structures of homologs. Thermal stability for nematic is 182.89°C, whose mesophase lengths minimum to maximum ranges from 17°C to 45°C and it is an upper middle ordered melting type series. Group efficiency order for nematic is series 1 > series Y > series X, as derived from comparative study of structurally similar analogous series.     

The Effect of Trifluoromethyl and Difluoromethoxy Groups on Mesomorphic Properties

Abstract

This paper describes the effect of terminal substituent on the mesomorphic properties in 3-and 4-(4-alkoxyphenoxycarbonyl)phenyl 3- and 4-R-benzoate and 4-(4-alkoxybenzoyloxy)phenyl 2-, 3-, and 4-R-benzoates (R = CF₃, OCF₃, OCF₂H). The meta-trifluoromethoxy and para-difluoromethoxy compounds tend to show a smectic C phase, as well as smectic A and nematic ones, and introduction of a chiral carbon in the alkoxyl group induces the chiral smectic C one.     

Mesomorphism Dependence on Molecular Structure

A novel homologous series of liquid crystal (LC) derivatives of general structure: RO·C₆H₄·COO·C₆H₃·OCH₃(ortho)CH = CH·COO·(n)C₅H₁₁ was synthesized and studied with a view to understanding the effect of molecular structure on liquid crystal behavior with reference to lateral –OCH₃ and terminal end group. Homologous series consists of 12 derivatives (C₁–C₁₆), the first five (C₁–C₅), and the last (C₁₆) members are not liquid crystals and the rest of the homologs (C₆–C₁₄) are enantiotropically smectogenic without exhibition of the nematic phase. The textures of the smectic phases are focal conic fan shaped or batonets of smectic-A or smectic-C. Average thermal stability for smectic is 81.8°C and mesophase length ranges from 9°C to 31°C. Transition curves of a phase diagram (Sm-I and Cr-Sm/I) behave in a normal manner. The Sm-I transition curve exhibits an odd-even effect. Analytical and spectral data support the molecular structures. The series is smectogenic of a middle ordered melting type. LC properties of the present series are compared with structurally similar known homologous series. Transition temperatures were determined by an optical polarizing microscope equipped with a heating stage.     

Studies on Anisotropic Molecular Orientation and Mesophase Stability in a Ternary Mixture of Liquid Crystalline Materials

The multicomponent system of cholesteryl linolenate (CL), sodium oleate (Naol), and orthophosphoric acid (H₃PO₄) exhibits liquid crystalline mesophases, like cholesteric and smectic phases, such as SmA, SmC, SmB, and SmG sequentially when the specimen is cooled from its isotropic phase. These phases have been observed by using microscopic technique. Helfrich potential and elastic moduli have also been estimated in the smectic phase using Helfrich model. Optical transmittance and electrical conductivity have also been discussed.     

Mesomorphism dependence on molecular rigidity and substitution of same functional group on lateral or terminal position of tailed phenyl ring

Novel liquid crystal materials (LCs) of low temperature range (53°C to 75°C) have been synthesized through a series of chalconyl derivatives consisting of two phenyl rings bonded through a –CH?CH?CO? central bridge to study the effect of molecular structure on LC properties in general and with a focus on molecular rigidity. The novel homologues series (C₁ to C₁₈) consists of thirteen homologues with general formula RO?C₆H₄?CH?CH?CO?C₆H₄?OC₁₀H₂₁(n) (meta). The C₁, C₂, C₃ homologues are nonliquid crystals (NLC) and the rest of the homologues (C₄ to C₁₈) are either monotropic or enantiotropic liquid crystals. C₄ to C₆ homologues are enantiotropicnematic and the rest of the mesomorphic homologues are (C₇ to C₁₈) monotropicsmectic in addition to monotropicnematic character. Transition and melting temperatures including textures of homologues were determined by an optical polarizing (POM) microscopy equipped with a heating stage. Textures of a nematic phase are threaded or Schlieren, and that of the smectic phase are of the type Smectic A or C as judged directly from the heating top of the microscope. Thermal stability for smectic is very poor and of the nematic is (N-I) 69.3°C whose, total mesophase length ranges between 07.0 to 14.0°C at C₈ and C₄ homologues respectively.     

Dependence of mesomorphism on tail group in combination with a lateral methoxy group

A novel homologous series of esters with a lateral methoxy group and terminal n-heptyl cinnamate group was synthesized and studied to investigate mesomorphic behavior in relation to structure. The twelve membered series consists of methoxy to pentyloxy derivatives that are nonmesomorphic and the rest of the homologs as smectegenically mesomorphic, including C₆ and C₇ monotropic smectic and C₈ to C₁₆ enantiotropic smectic without exhibition of any nematic property. The textures of smectogenic mesophases are focal conic fan shaped or batonates of the type smectic-A or Schlieren-C. An odd-even effect is exhibited by the Sm–I transition curve in the phase diagram. The Cr–Sm and Sm-I transition curves behave in a normal manner. Transition temperatures and textures were determined on an optical polarizing microscope, equipped with a heating stage. Some representative members were characterized by IR, H¹NMR, mass spectra, and elemental analysis. Analytical data support the molecular structures of the homologs. Mesomorphic properties of the present novel series are compared with the structurally similar known series. The present series is smectogenic only, whose thermal average stability is 89.8^°C and of a middle-ordered melting type.     

Molecular flexibility dependence mesomorphism

A novel series of chalconyl homologue derivatives with RO.C₆H₄.COO.C₆H₄.CO.CH:CH-C₆H₄.N.(CH₃)₂ (Para) have been synthesized and thermotropically studied with a view to understanding and establishing the effect of molecular structure on mesomorphic behavior of the novel homologues. The series consists of thirteen homologues (C₁ to C₁₈). C₇ to C₁₈ homologues are smectogenic, C₄ to C₁₈ nematogenic and C₁ to C₃ nonmesomorphic. Thus, novel chalconyl series is predominantly nematogenic and partly smectogenic. Transition temperatures and textures of mesophases were determined using an polarizing optical microscope (POM) equipped with a heating stage. Analytical and spectral data confirmed molecular structures of homologues. Phase transition curves showing phase behavior in a phase diagram behaved in normal manner. Thermal stability for smectic and nematic are relatively low at 59.6 °C and 76.6 °C respectively whose, smectogenic and nematogenic phase length vary from 12 to 16 °C and 06 to 20 °C, respectively. Mesomorphic behaviors of the present series are compared with a structurally similar known homologous series.     

Transitions de Phase en Series Mesogenes:

The polymorphism of the di(4-alkylphenyl) and di(4-alkoxyphenyl) tetrathiafulvalene (TTF) is investigated by optical, crystallographic and calorimetric methods. All the studied derivatives are mesomorphic. The first mesophase is always a smectic G phase; the second one is a nematic N phase for short chains and a smectic C phase for long chains.

The entropies corresponding to the passage high-temperature crystalline phase C₁ → S_G and to the “melting” (C₁ → mesophases → isotropic phase I) increase with the length of the chain and with the presence of the oxygen atom in the radical.     

Synthesis and study of mesomorphic properties in rod-like chalconyl compounds

In order to investigate the influence of the central linking group and effect on flexibility on mesophase behavior of liquid crystal we have synthesized newly homologous series viz. 3-(4-Octyloxyphenyl)-1-(4′-n-alkoxy phenyl) prop-2-en-1-one (Series-l) consists of thirteen homologues (C₁ to C₈, C₁₀, C₁₂, C₁₄, C₁₆, C₁₈). Textures of a nematic phases are threaded or Schlieren type. The textures of smectic and nematic phase are directly judged from the heating and cooling condition. Group efficiency order for mesophases is derived on the basis of thermal stabilities from the comparative study of thermometric data determined from structurally analogous series. A transition curve as depicted in a phase diagram behaves in normal manner. Structural and conformational characterization of these new compounds had achieved by ¹H NMR, ¹³C NMR, IR, and elemental analysis.