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.     

Synthesis and Mesomorphic Characteristics of Fluoroaniline Derivatives with Different Lateral Groups

Two new homologous series of liquid crystals viz. 4-(4'-n-alkoxybenzoyloxy)-2-chlorophenylazo-4”-fluorobenzenes(I) and 4-(4'-n-alkoxybenzoyloxy)-2-methylphenyl azo-4”-fluorobenzenes(II) with terminal fluoro, lateral chloro(I) and methyl(II) group and central ester and azo linkages are synthesized and their mesomorphic properties are studied. Both the series are similar in molecular structure with the difference in their lateral substitutions; series I has chloro group and series II has methyl group as laterally substituted groups. All the twelve homologues of each of the series are mesogenic in nature. Series I shows nematic mesophase from the first C₁ to the last C₁₆ derivative synthesized; smectic mesophase is exhibited by last two viz. C₁₄ and C₁₆ derivative, where as all the members from C₁ to C₁₆ of series II only show nematic mesophase. The nematic mesophase shows marble texture and the smectic mesophase shows Schlirene texture of the Smectic C variety. Both the series are compared with structurally related series.     

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.     

Mesomorphism in chloro substituted isomeric series including chalconyl central bridge

A novel homologous series of thermotropic liquid crystals α-4-(4′-n-alkoxy benzoyloxy phenyl) β-2″-chloro benzoyl ethylenes have been synthesized and studied with a view to understand and establish the effect of molecular structure on liquid crystal (LC) properties with reference to molecular flexibility in isomeric series with differing positional status of same functional group. Novel homologues series consist of 12 homologues C₁ to C_16. C₁, C₂, and C₃ homologues are nonliquid crystals (NLC) and rest of the homologues are liquid crystals. C₁₀ to C₁₆ homologues are enantiotropically smectogenic plus nematogenic and C₄ to C₈ homologues are enantiotropic nematic. The texture of nematogenic derivatives is threaded or schlieren and that of the smectic mesophase are focal conic of the type smectic A or C. Analytical, thermal and spectral data supported molecular structures of novel homologues. Transition temperatures as determine by a hot stage polarizing optical microscopy (POM) were plotted against number of carbon atom present in n-alkyl chain ‘R’ of left n-alkoxy (-OR) group and the phase transition curves Cr–I/M, Sm–N, N–I were obtained on linking like or related points. The odd–even effect is observed for the N–I transition curve and thus transition curves behaved in normal manner. The even-membered nematic transition curve occupied higher position than the odd-membered transition curve. Present series is predominantly nematogenic and partly smectogenic with middle-ordered melting type.     

Dependence of mesomorphism on geometrical shapes of isomeric and nonisomeric series of chalconyl esters

A meta substituted chalconyl ester homologous series: RO?C₆H₄?COO?C₆H₄(meta)?CO?CH?CH?C₆H₄?OC₁₂H_25(n)(para) is synthesized and studied with a view to understanding the effect of molecular substitution at meta position in a molecular structure on thermotropic liquid crystal properties. The novel homologous series consists of thirteen homologues (C₁ to C₁₈). All the homologues except the nonliquid crystal homologues C₁, C₂, C₃ are enantiotropic nematic with the absence of smectic properties. The transition and melting temperatures were determined by an optical polarizing microscopy (POM) equipped with a heating stage. Textures of a nematic phase are threaded or Schlieren. Transition curves (Cr-N/I and N-I) behave in normal manner except homologues between C₁₀ and C₁₄ of N-I curve, which show negligible deviation from normal and a smooth descending tendency. The N-I transition curve exhibits an odd-even effect up to C₁₀ homologue and then the odd-even effect disappears for higher homologues. Analytical and the spectral data support the molecular structures. Thermal stability for nematic is 107.3°C and the mesophase lengths range between 13.0°C and 35.0°C at the C₁₈ and C₁₂ homologues respectively. Group efficiency order for nematic is derived on the basis of thermal stability as ?OC₁₂H_25(n) (linear) > ?OC₁₂H_25(n) (nonlinear) > ?OC₁₆H₃₃ (nonlinear).     

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 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.     

Synthesis and mesomorphic properties of 2,4-bis(4′-n-pentyloxybenzoyloxy)- benzylidine-4″- n-alkoxyaniline

The synthesis and mesomorphic properties of a new series of 2,4-bis(4′-npentyloxybenzoyloxy)- benzylidine-4″ -n-alkoxyaniline (DC5An) are reported. The molecular structure of compounds was confirmed by FTIR, ¹H-NMR, ¹³C-NMR, mass spectroscopy and elemental analysis. The mesomorphic properties were studied by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) measurements. All compounds of the series exhibit nematic (N) and smectic C (SmC) phases. The first four homologues (DC5A1-DC5A4) display a N mesophase, whereas the highest homologues (DC5A5-DC5A10) exhibit an enantiotropic dimorphism N and SmC phases. The mesomorphic properties of the present series are compared and discussed with other structurally related series.     

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).     

Molecular flexibility dependence on mesogenic behaviors of isomeric and nonisomeric series

A novel homologous series containing vinyl ester and azomethane central bridges and n-alkoxy as well as 3″,4″-dimethyl groups as flexible terminal/lateral groups viz. RO?C₆H₄?CH = CH?COO?C₆H₄?N?CH?C₆H₃-(CH₃)₂ have been synthesized and studied with a view to establishing the relation between molecular structure and thermotropic liquid crystal (LC) properties with reference to molecular flexibility within the series. The series consists of twelve homologues (C₁ to C₁₆). C₆ and C₇ homologues are smectogenic plus nematogenic and C₈ to C₁₆ homologues are only smectogenic, and the rest of the homologues (C₁ to C₅) are nonmesomorphic. Transition temperatures and the textures of the homologues were determined using an optical polarizing microscope equipped with a heating stage (POM). The textures of a nematic phase are threaded or Schlieren and that of a smectic phase are of the A or C type. Analytical, thermal and spectral data support the molecular structures. Smectic and nematic thermal stabilities are 116.85°C and 147.5°C, respectively. Whose Sm?N/I and N-I mesophase lengths are varied between 15°C to 21°C and 25°C to 62°C, respectively. The novel compounds are compared with structurally-similar series.     

Synthesis of novel azoester homologous series of liquid crystalline behavior and the study of mesomorphism dependence on lateral substitution of middle phenyl ring

The titled azoester liquid crystalline homologous series consists of eleven homologues. The pentyl to tetradecyl derivatives of the series are nematogenic without exhibition of smectogenic character. Rest of the members of the series are nonliquid crystalline in nature. Textures of the nematic mesophase are schlieren or threaded type. Transition curves in the phase diagram showed normal phase behavior. Transition temperatures and liquid crystal behavior observed under an optical polarizing microscope equipped with a heating stage. An odd even effect is observed for nematic-isotropic transition curve. Analytical and spectral data confirms the structures of the molecules. Present homologous series is predominant nematogenic and partly nonmesogenic. Average thermal stability for nematic is 125.33°C and nematogenic mesophase length varies between 12°C to 48°C at tetradecyl (C₁₄) and octyl (C₈) derivatives, respectively.     

Study of deviation from normal liquid crystal behavior of mesomorphic-isotropic transition curve in a chalconyl ester series with equipolar terminal end groups

A novel chalconyl ester homologous series RO.C₆H₄.COO.C₆H₄.CO-CH:CH-C₆H₄.OC₈H₁₇(p) synthesized and studied with a view to understanding and establishing the relation between molecular structure and Liquid Crystal (LC) properties of thermotropic mesomorphs. The novel series consists of eleven homologous (C₁ to C₁₆). Enantiotropicnematic type of mesophase formation commences from C₃ homologue and continued up to the last C₁₆ homologue of a novel series. Smectogenic character is totally absent for the novel series. Transition temperatures and the textures of nematic phase were determined through an optical polarizing microscopy (POM) equipped with a heating stage. Textures of nematic phase are threaded or Schlieren. Transition curve Cr-N/I and N-I behaved in normal manner except C₈ homologue which showed negligible deviation from normal behavior. N-I transition curve exhibited odd–even effect. Analytical and structural data supported the molecular structures of homologues. Average thermal stability for nematic is 98.88°C whose degree of mesomorphismvary from 12.0°C to 37.0°C. Evaluated thermometric data of present novel series are compared with structurally similar series. Group efficiency order for nematic on the basis of thermal stability, early commencement of mesophase and the degree of mesomorphism. Thus, present series is predominantly nematogenic and lower middle ordered melting type the low degree of mesomorphism.     

Synthesis and Evaluation of Liquid Crystal Behavior of a Novel Homologous Series: 4-(4′-n-Alkoxy benzoyloxy) Phenylazo-2″, 6″-dimethylbenzenes

A novel homologous series entitled 4-(4′-n-alkoxy benzoyloxy) phenyl azo 2^″, 6^″-dimethyl benzenes consisting of 12 members is reported. Liquid crystal behavior as a nematogenic mesophase commences from the pentyloxy homologue monotropically and then continues enantiotropically until the last hexadecyloxy homologue without exhibition of any smectogenic behavior. An odd-even effect is observed for nematic-isotropic transition curve of the phase diagram. The textures of the nematic mesophase are of the threaded or Schlieren type. Analytical and spectral data support the molecular structure of the homologues. Transition temperatures of the novel homologues were determined by an optical polarizing microscopy. Liquid crystal properties of a novel homologous series are compared with other known homologous series. The average thermal stability for the nematic phase is 77.1°C.     

Role of n-alkoxy terminal end groups on mesomorphism

A homologous series RO-C₆H₄-CH:CH-COO-C₆H₄-CO-CH:CH-C₆H₄-OC₆H₁₃ (n) of novel liquid crystals (LC) has been synthesized and studied with a view to understanding and establishing the relation between molecular structure of a substance and the LC properties or behavior of thermotropic LC materials. Novel series consist of 11 homologues. C₁ and C₂ homologue derivatives are non-LCs and the rest of homologues (C₃ to C₁₆) are nematogenic without exhibition of smectic property. Transition temperatures were determined by an optical polarizing microscopy equipped with a heating stage. Transition curve Cr-N/I of a phase diagram behaved in normal manner. N/I transition curve partly deviated at C₆ and C₁₀ homologues from normal descending behavior, and exhibited very narrow and sharp odd-even effects. Textures of nematic phase are threaded or Schlieren. Thermal, analytical, and spectral data confirmed the molecular structures of novel chalconyl ester derivatives. Thermal stability for nematic is 95.77°C and the upper and lower mesophase lengths vary from 35 to 16°C at C₅ and C₈ homologues respectively. Group efficiency order derived for nematic on the basis thermal stability is -OC₁₀H₂₁ (n) > -OC₈H₁₇(n) > -OC₆H₁₃(n).     

Mesomorphic dependence on molecular rigidity by central bridge and homo–hetero ring systems

A novel homologous series of thermotropic derivatives containing a heterocyclic ring was synthesized and studied with a view to understanding and establishing a relation between liquid crystal (LC) properties and the molecular structure of chalconyl derivative in general. The series comprises 12 homologues, of which smectogenic LC property commences from the decyloxy (C₁₀) homologue and continues for C₁₂, C₁₄, and C₁₆ homologues. Homologues C₁ to C₈ are non-liquid crystals. Exhibition of nematogenic mesophase is totally absent. Transition and melting temperatures were determined by an optical polarizing microscope equipped with a heating stage. Spectral and analytical data confirmed the molecular structures of homologues. The textures of smectic mesophase are A or C, and are determined by a miscibility method. The average thermal stability of the smectic phase is 113.57°C. The mesogenic phase length ranges between 4.1°C and 11.1°C. Thus, it is a middle-ordered melting-type series of shorter range of liquid crystallinity with absence of nematogenic character. Some LC properties of the present series are compared with a structurally similar known homologous series.     

Synthesis,Characterization and Mesomorphic Properties of New Rod-like Thiophene Based Liquid Crystals

Two new mesogenic homologous series of Schiff base esters, 2-[4-(4′-n-Alkoxy benzoyloxy) benzylidenamino] 3-cyno thiophine (Series-A) and Schiff base cinnamates, 2-[4-(4′-n-alkoxy cinnamoyloxy) benzylidenamino] 3-cyano thiophene (Series-B), comprising a thiophene moiety were synthesized. Structural elucidation was carried out using elemental analysis and spectroscopic techniques such as FT-IR, ¹H-NMR and ¹³C-NMR, and mass spectrometry. The mesomorphic properties and thermal stabilities of the title compounds were studied by using differential scanning calorimetry and optical polarizing microscopy. All the derivatives are mesomorphic in nature showing the nematic phase, and the higher members of Series-A show a smectic C phase whereas Series-B exhibits only the nematic mesophase. The mesomorphic properties of the present series are compared with other structurally related compounds.     

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.     

Mesomorphism dependence on heterocyclic tail

A novel homologous series of liquid crystal materials containing a heterocyclic ring was synthesized with a view to understanding and establishing the relation between liquid crystal (LC) properties and a molecular structure; and with a view to curing skin-related diseases following biological activity studies. The series consist of 13 (C₁ to C₁₈) members. All the members are liquid crystals. The C₄ to C₁₈ members are smectogenic of which C₄ and C₅ are monotropic and remaining members (C₆ to C₁₈) are enantiotropic in nature; whereas all C₁ to C₁₈ members are enantiotropically nematogenic. Hence the C₁, C₂, C₃ members are only nematogenic and the rest of the homologues are smectogenic in addition to nematogenic. Transition temperatures were determined by an polarizing optical microscope equipped with heating stage. Analytical and spectral data confirmed the molecular structures of homologues. It is a middle ordered melting type series. LC properties of a series are compared with the structurally known series.