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 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.     

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).     

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.     

Synthesis and characterization of rigid rode shape homologous series: Effect of tail iodo group

Arylpiperazine derivatives referred in this article possessed antitumor activity, which were synthesized and crystallized through the gradual evaporation process. The molecular structures of 2-(4-(2-(4-phenylpiperazin-1-yl)ethyl)benzyl)isoindoline-1,3-dione (C27H27N3O2, 1), 2-(4-(2-(4-(4-bromophenyl)piperazin-1-yl)ethyl)benzyl)isoindoline-1,3-dione (C27H26BrN3O2, 2) and 2-(4-(2-(4-(4-chlorophenyl)piperazin-1-yl)ethyl)benzyl)isoindoline-1,3-dione (C27H26ClN3O2, 3) were determi-ned and described. π-π interactions were observed in the packing modes of three compounds, and compound 2 and 3 showed halogen interactions between molecules nearby, which were different from compound 1. The dihedral angle values, the bond lengths, bond angles and the parameters demonstrated that involvement of halogen atoms did affect the conformation, configuration and cell parameter of the compounds.     

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.     

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.     

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.     

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.     

Synthesis and Mesomorphic Behavior of Calamitic Liquid Crystals with a Biphenyl Moiety

A new mesogenic homologous series having a biphenyl moiety has been synthesized by condensing 4-hydroxy-4′-nitrobiphenyl- and methoxy-substituted 4-n-alkoxy cinnamoyl chlorides, and their liquid crystalline properties have been studied. All the members of the series are enantiotropic liquid crystals. The methyl to n-pentyl derivatives exhibit both Smectic A (SmA) and Nematic (N) phases; the higher members, starting with the n-hexyl derivative show only a SmA phase. The plot of transition temperatures versus number of carbon atoms in the alkoxy chain exhibits zig-zag pattern for Sm-N and N-Isotropic (Iso) transition temperature curves. The average thermal stability is compared with other related homologous series. The introduction of polar nitro group increases significant intermolecular force of attraction which stabilizes the molecular orientation. This results into the increase in the thermal stability of the system.     

Mesomorphism of azo-esters and chalcone-esters

One chalcone-ester homologous series of mesogens α-4-[4^/-n-alkoxybenzoyloxy phenyl β-4^//methoxy benzoyl ethylenes (A) and one azo-ester homologous series of mesogens p-(p^/-n-alkoxybenzoyloxy) phenyl azo-p^//-methoxy benzene (B) being structurally similar are discussed. Both series (A) and (B) differ in respect of central bridges linking two phenyl rings. Mesomorphic properties start from 6th and 1st member of series (A) and (B) respectively. In series (A), 6th to 12th members show both smectogenic and nematogenic properties, and the 14th and 16th members show only nematogenic property. While in series (B), 1st to 10th members show nematogenic properties, 11th member shows both smectogenic and nematogenic properties, while 12th member shows only smectogenic property. Thermal stability of series (A) is relatively high as compared to series (B). Transition temperatures are observed through hot stage polarizing microscope by the miscibility method. Analytical data support the structure of molecules. Textures of series (A) in nematic are threaded and Schlieren in SmecticSmectic A type, while that of series (B) in nematic are threaded in SmecticSmectic A and smectic C.     

Mesomorphic properties of liquid crystalline compounds with chalconyl central linkage in two phenyl rings

In order to investigate the influence of the central linking group and the effect of flexibility on mesomorphism, we have synthesised a newly homologous series 3-(3-butoxyphenyl)-1-(4-n-alkoxy phenyl) prop-2-en-1-one (series-l) consisting of 13 homologues C₁–C₈, C₁₀, C₁₂, C₁₄, C₁₆ and C₁₈. In the present series, mesophase commences from the C₆ homologue. C₁–C₅ homologues did not exhibit liquid crystalline (LC) property, while C₆–C₁₂ homologues exhibited an enantiotropic nematic phase and the rest of the homologues C₁₄–C₁₈ displayed monotropic SmC and nematic mesophase. The transition temperatures of the synthesised compounds were determined by an optical polarising microscopy equipped with a heating stage. All newly synthesised compounds were confirmed by ¹H-NMR, ¹³C-NMR, IR and elemental analysis.     

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 Properties of New T- Shaped Dimesogens

Abstract

Several new T- shaped liquid crystalline dimesogenic compounds were synthesized and their LC properties were characterized. These T-shaped dimesogens consist of substituted fluorene and substituted biphenyl units connected by flexible spacer units of varying lengths. The compounds were characterized for their liquid crystallinity by differential scanning calorimetry (DSC) and polarizing microscopy. All the compounds were found to exhibit enantiotropic nematic phase.     

The effect of position of octadecyloxy tail on the formation of liquid crystal with chalconyl-ester and chalconyl-vinyl ester series: Comparison with corresponding linkage group

Understanding of the electronic structures is indispensable for complete elucidation of the charge carrier behaviors in organic semiconductors. Although recent progress enabling accurate photoemission demonstrations of organic single crystals has greatly promoted such understanding, it had been achieved merely on partially oxidized surfaces by exposure to ambient conditions. In this study, we successfully prepared an oxide-free surface of the pentacene single crystal (PnSC) by cleavage in vacuum. X-ray and ultraviolet photoelectron spectroscopy measurements on the PnSC clean surface revealed improved energetic homogeneity of the C1s level and highest-occupied state in comparison to those of the partially oxidized surface.     

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.