Effect of Nitro Terminal Substituent on the Liquid Crystalline Characteristics of Ester Mesogens: p-Nitrophenyl-p'-n-Alkoxycinnamates

The homologous series p-nitrophenyl-p'-n-alkoxycinnamates is a medium melting homologous series; the first two members are non-mesogens and do not exhibit even monotropy. The nematic phase begins from the third derivative in monotropic condition; from the fourth member enantiotropic mesomorphism commences. Polymesomorphism begins from the sixth member with the appearance of smectic mesophase and ends at the seventh member. The rest of the homologues up to the octadecyl are purely smectogens. Thus the homologous series is predominantly smectogenic even though -NO₂ group is reported to be enhancing nematic character.^' Within the polymesomorphic region the nematic mesophase is homeotropic; however, it shows a clear threaded texture where it is the only mesophase shown. The N-I transitions do not exhibit the usual alternation in transitions which is a rare phenomenon. The N-I transition curve is unusually neither rising nor falling though a slight curve is seen; it merges with the S-I curve which shows a slight rising tendency as the alkyl chain length is increased. The S-N transition curve steeply rises and seems to be merging with the S-I curve. The mesomorphic range is good; the nature of the curve can predict the latent N-S or I-N transitions. All smectic orientations are of focal conic smectic A texture except in the case of sixth and seventh homologues where homeotropic nature prevails.     

Study of relation between liquid crystal properties and molecular structure of halogenated benzyl alcohol ester derivative

Comparison among the structurally similar analogous or isomeric novel homologous series of presently investigation is discussed with a view to understand the effect and relation between molecular structure in respect of molecular size, geometrical shape, molecular polarity and polarizability etc as emerged from changing molecular rigidity and flexibility which is played by terminal or central bridge to inducing liquid crystal property and the specific degree of mesomorphism of a substance. Novel series of study consists of three phenyl rings, two central bridges ?COO?, ?CH?CH?COO?, ?COO?CH₂?, ?CH?CH?COO?CH₂? with common left n-alkoxy (?O?C_nH_{2n + 1}) left terminal group which vary from homologue to homologue in the same series and varying tail end group –Cl and –Br. Novel members of series were selectively characterized and confirmed by elemental analysis, IR spectra, H¹NMR spectra, mass spectra, POM, textures of smectic or/and nematic phase by miscibility method etc. Totally 66 novel compounds were synthesized and 55 compounds were to be found liquid crystal (LC) in nature with different degree of mesomorphism depending upon changing molecular structure in respect of their tailed flexible end groups or central bridges.     

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.     

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.     

Synthesis and Study of New Mesogens II: p-(p′-n-Alkoxycinnamoyloxy)-benzylidene p″ -anisidines (1) and p-(p′-n-Alkoxycinnamoyloxy)- benzylidene anilines (2)

Two new homologous series of liquid crystals viz. p-(p'-n-alkoxycinnamoyloxy) benzylidene p”-anisidines (1) and p-(p'-n-alkoxycinnamoyloxy) benzylidene anilines (2) comprising twenty four mesogens have been synthesized. Both are high melting series of mesomorphs. In the homologous series (1) the nematic mesophase is exhibited from the very first member; however, the first five compounds decompose at high temperatures before passing into isotropic liquid condition. Polymesomorphism is exhibited with the appearance of the smectic mesophase at the octyl derivative and remains up to the last viz. octadecyl homologue. Within polymesomorphic region the nematic mesophase is homeotropic; however, it shows a clear threaded texture where it is the only mesophase shown i. e. in the first seven members of the homologous series (1). The smectic mesophase shows focal conic fan shape texture belonging to smectic-A variety. The nematic-isotropic curve shows descending tendency as the series is ascended-a characteristic of high melting series. The smectic-nematic transition curve rises steeply and shows a levelling off tendency at the octadecyl derivative. In the homologous series (2), no decomposition occurs. The smectic mesophase commences a little early i. e. from hexyl derivative; while polymesomorphism is clearly exhibited up to the dodecyl derivative, the last two homologues are purely smectogens. The usual odd-even effect is observed in case of the nematic-isotropic curve for series (2). The smetic-nematic curve rises gradually and seems to be merging with the falling nematic-isotropic curve at the fifteenth homologue. The mesomorphic ranges in both series are quite wide; however, that of series (1) is wider than one obtained in series (2). Thermal stabilities are good and are in keeping with the molecular characteristics. The textures of the smectic and nematic mesophases are similar to that of the series (1). Both series are comparable with each other and other related series.     

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.     

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.     

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.     

Study of mesomorphism and its relation to molecular structure with special reference to central bridges viz. -COO- and -CH=CH-COO- of the homologous series

Two ester homologous series of mesogens, viz., Methyl-p-(p′-n-alkoxy benzoyloxy) cinnamates (X) and Methyl-p-(p′-n-alkoxy cinnamoyloxy) cinnamates (Y) being structurally similar are discussed. Both (X) and (Y) differ in respect of central bridges linking two phenyl rings. Only enantiotropic nematogenic character is observed without exhibition of any smectic character by all members of series (X) and (Y). Thermal stability of series (X) is relatively low as compared to (Y), but nematogenic mesophase lengths are of reverse order. Solid-nematic/solid-isotropic and nematic-isotropic transition curves in the phase diagrams behave in normal manner.     

Effect of the Terminal Substituents on the Smectic Layer Spacings in 4-(trans-4′-n-Alkyleyelohexyl) Benzoates

The spacings of the smectic layers are compared with the lengths of molecules of p-substituted phenyl 4-(trans-4′-n-decylcyclohexyl) benzoates. It has been found that if the NO₂, CN or CHO groups are substituted in the p-position of the phenyl, then the smectic layers consist of dimers, whereas in the presence of the NCS, COCH₃, I, Cl, Br, F substituents the smectic layers reveal a monomolecular spacing.     

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.     

Study of a new homologous series of liquid crystals: Isopropyl-p-(p/-n-alkoxy cinnamoyloxy) cinnamates

A new homologous series: isopropyl-p-[p^/-n-alkoxy cinnamoyloxy] cinnamates was synthesized and studied with a view to understanding and establishing the relation between liquid crystal property and molecular structure. Twelve homologues were synthesized. Methyl to butyl homologues are not liquid crystals, while pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, and hexadecyl derivatives are enantiotropic liquid crystal in nature with nematogenic character. Smectogenic character is totally absent. A phase diagram is obtained by plotting a graph of transition temperatures versus number of carbon atoms is n-alkyl chain of left n-alkoxy terminal end group. Solid-isotropic or solid-nematic transition curve rises steeply from methyl to propyl derivatives and falls to pentyl homologue through butyl homologue, and follows a zigzag path of rising and falling values as the series is ascended. Nematic–isotropic transition curve shows descending tendency as series is ascended in a normal manner with exhibition of odd-even effect. Smectic mesophase does not appear even in the monotropic condition. Phase transition temperatures are determined by hot stage polarizing microscope. Analytical data support the structure of molecules. Texture of nematic mesophase is of threaded type. Mesomorphic properties are compared with structurally similar homologous series.     

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.     

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 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.     

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.     

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     

Mesomorphic and DFT studies of terminal ester containing salicylaldimines and their copper (II) complexes

In this article, we report synthesis and characterization of a novel homologous series of butyl 4-(4′-(alkoxy)-2-hydroxybenzylideneamino)benzoates, C_nLH (n = 6, 8, 10, 12, 14, 16) and their copper(II) complexes. The mesomorphic properties of these compounds were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and powder X-ray diffraction (XRD) studies. The ligands and their copper(II) complexes exhibit wide range of enantiotropic smectic A mesophase as confirmed by their typical optical texture under polarizing microscope. Thermal stability of the compounds is determined by thermo gravimetric analyses. DFT calculations have been performed using GAUSSIAN-09 program at B3LYP level to obtain the stable electronic structure of the ligand and its copper(II) complex.     

Synthesis and Liquid Crystal Behavior of a Novel Ester Homologous Series

A novel ester homologous series of 4-[4’-n-alkoxy cinnamoyloxy] benzyl benzoates has been synthesized. The series consists of 12 homologues. Liquid crystal properties commence from the sixth member to the last member of the series with the exhibition of an enantiotropic nematic phase without the exhibition of any smectogenic mesophase. The remaining homologues do not exhibit liquid crystal behavior. The texture of the nematic phase is of the threaded or Schlieren type. The solid-nematic or isotropic transition curve adopts a zigzag path and the nematic-isotropic transition curve steeply rises and then falls in the phase diagram and behaves in normal manner. An odd–even effect is absent in the nematic-isotropic transition curve with an alteration of transition temperatures. The average thermal stability for the nematic mesophase is 153.1°C, and the nematogenic temperature ranges vary from 12°C to 50°C. Analytical data confirm the molecular structures of the homologues. The Liquid Crystal properties and transition temperatures were observed through an optical polarizing microscope, equipped with a heating stage. The mesomorphic characteristics of the novel ester series are compared with other, known and structurally similar series. The novel series is predominantly nematogenic with the absence of any smectogenic character, with relatively short mesophase temperature ranges and of the middle ordered melting type.     

Smectic phases of liquid crystals based on dinuclear palladium(II) complexes with carboxylato bridge

In this paper we present the preparation and the investigation of the liquid crystal properties of a series of dinuclear carboxylato bridge Pd(II) complexes bearing six alkoxy peripheral chains in the molecule. Their structures were assigned based on elemental analysis, IR and ¹H NMR spectroscopy whereas the thermal behaviour was investigated by polarizing optical microscopy and differential scanning calorimetry. The monotropic smectic A phase displayed by these materials was identified by miscibility studies with a previously reported mesogen. It was found that the transition temperatures and the SmA mesophase stability depend on the alkyl chain length of the carboxylato bridge. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)