Nonliquid Crystals Research Articles

Impact of the terminal fluorination of bisthienylethene-based liquid crystals on the self-assembly and mechanochromic behaviors

Four novel bisthienylethene-based rod-like liquid crystals containing different numbers of terminal fluorine atoms were designed and the effect of the terminal fluorination on liquid crystalline self-assembly, optical characteristics in solid state and mechanochromic behaviors was explored. The transition from non-liquid crystal via monotropic liquid crystal with smectic A phase to enantiotropic liquid crystal with smectic A phase can be achieved and the temperature ranges of smectic A phase gradually increase by increasing the terminal fluorination, which might be due to the increase in intermolecular interactions by increasing the number of terminal fluorine atom. All the compounds exhibited AIE characteristic and distinct solid-state fluorescence with yellow or orange color. In addition, the non-fluorosubstituted and difluorosubstituted bisthienylethene-based liquid crystals exhibited reversible mechanochromism, whereas the monofluorosubstituted and trifluorosubstituted bisthienylethene-based liquid crystals exhibited extremely weak mechanochromism due to different intermolecular interaction, molecular symmetry and molecular conformation. These investigations implied that the incorporation of fluorine atom could result in interesting self-assemblies and photophysical properties in different states, which also provided the understanding of the relationship between chemical structures and properties.

Crystal structure and Hirshfeld surface analysis of 3-({4-[(4-cyano-phen-oxy)carbon-yl]phen-oxy}carbon-yl)phenyl 4-(benz-yloxy)-3-chloro-benzoate.

The title compound, C35H22ClNO7, is a non-liquid crystal with a bent-shaped mol-ecule. The dihedral angles between adjacent aromatic rings in the mol-ecule (starting from the cyano-benzene ring) are 72.61 (2), 87.69 (4), 64.08 (2) and 88.23 (2)°, indicating that adjacent rings are close to perpendicular to each other. In the crystal, the mol-ecules are linked by weak C-H⋯N and C-H⋯π inter-actions, thereby forming a two-dimensional supra-molecular architecture in the ac plane. The most important contributions to the crystal packing arise from H⋯H (59.3%), S⋯H (27.4%) and O⋯H (7.5%) inter-actions, as determined by a Hirshfeld surface analysis.

“Synthesis and study of novel biological active chalconyl-ester based bent-core LCs: Effect of tail/lateral group”

A newly designed homologues series: 4-bromo-2-(3-(4-dimethyl amino) phenyl) acryloyl)-6-nitrophenyl-3-(4-n-alkoxy phenyl) acrylate has been synthesized and studied through chalconyl vinyl ester linking group at (ortho) position. Novel series consisted thirteen compounds, in which C1 to C5 homologue are nonliquid crystal, while C6 to C18 exhibits SmC and nematic phase at enantiotropically manner. Thus, present novel series is predominantly nematogenic and partly smectogenic mesophase. Mesophase image of present compounds are schlieren like, broken fan and threaded type textures measured by POM equipped with heating stage. All this compounds were characterized by FT-IR and 1H NMR analysis. The mesomorphism is measured by POM, DSC and molecular packing is confirmed by XRD technique. Chalconyl ester based compounds C4 to C12 shows antibacterial as well as antifungal activity compared with corresponding standard drugs. Analytical and spectral data confirmed the molecular structures of the present V-shaped bent core homologous series.

Reducing the actuation threshold by incorporating a nonliquid crystal chain into a liquid crystal elastomer.

Liquid crystal elastomers (LCEs) are important smart materials that can undergo reversible deformation in response to liquid crystal (LC) phase transitions. A low threshold temperature for LC phase transition is advantageous because the LCE material can be more conveniently actuated by the applied stimulus. In this work, we investigated the effect of a nonliquid crystal chain on the reduction of threshold temperature of the LC phase transition by linking a nonliquid crystal side chain, 4-methoxyphenyl-1-hexenyloxy (MOCH3), to the network backbone of a classical polysiloxane-based side-chain nematic LCE. The nematic–isotropic transition temperature (Tni) of the MOCH3 incorporated nematic LCE was lower than that of the normal nematic LCE without the incorporation of a nonliquid crystal chain by about 27 °C. Compared to the normal nematic LCE or its nanocomposite, the MOCH3 incorporated nematic LCE or its nanocomposite demonstrated more rapid thermo-actuated deformation or photo-actuated deformation, and can be actuated to attain full axial contraction at an obviously lowered temperature or by light with obviously lowered intensity, while the maximum contraction ratio basically did not vary. These research results indicate that some nonliquid crystal chains show potential for improving the characteristics and enhancing the application significance of LCE materials.

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

ABSTRACTAn 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.

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

ABSTRACTNovel 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.

Mesomorphism in chloro substituted isomeric series including chalconyl central bridge

ABSTRACTA 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 C16. 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.

Role of molecular structural flexibility on mesomorphism

ABSTRACTA homologous series of novel chalconyl ester derivatives: RO.C6H4.COO.C6H4.CO.CH:CH.C6H4.OC6H13(n) shave been synthesized and studied for its thermotropic liquid crystal (LC) properties with a view to understanding and establishing the relation between molecular structure and LC properties. The homologous series consists of eleven members whose, mesomorphism commences from C3 of the series and continues up to the C16 homologue. The C1 and C2 homologues are nonliquid crystals. All the LC homologues are enantiotropically nematogenic with absence of smectogenic character. Transition temperatures were determined by an optical polarizing microscope (POM) equipped with a heating stage. Textures of a nematic phase are threaded or Schlieren. Analytical and spectral data confirms the molecular structures of homologues. Transition curve Cr-N/I behaved in normal manner. N-I transition curve exhibits an odd even effect; descended at C10 homologue and then again rises at C12 and descended from and beyond C12 homologue. Thus it partly deviates from normal behaviour. Thermal stability for nematic is 95–89°C and nematogenic upper and lower mesophase lengths are 41.0°C and 07.0°C respectively. Group efficiency order for nematic on the basis of thermal stability is –OC8H17(n)> -OC6H13(n) > -OC10H21(n) and it is a low order melting type series.

Dependence of mesomorphism on flexibility of lateral and terminal groups of chalconyl esters

ABSTRACTA novel liquid crystalline homologous series of chalconyl vinyl esters with a lateral bromo substituent RO─C6H4─CH═CH─COO─C6H3─(Br)─CO-CH═CH─C6H4─C12H25(n) has been synthesized and studied with a view to understanding and establishing the relation between the molecular structure and liquid crystal (LC) behavior in terms of molecular flexibility of the lateral and terminal groups. The novel homologous series consists of thirteen (C1–C18) homologues, whose enantiotropic nematic and smectic mesomorphism commences from the C4, (C4–C18) and the C5, (C5–C18) homologue, respectively. The rest of the homologues (C1, C2, C3) are nonliquid crystals (NLC). Mesomorphism and transition temperatures were examined using an optical polarising microscope (POM) equipped with a heating stage. Textures of nematic phase are threaded or Schlieren and those of the Smectic-A or Smectic-C are focal conic. Analytical, thermal and spectral data supported molecular structures of the novel homologues. Thermal for smectic and nematic are 87.5°C and 101.1°C, respectively, whose, total mesophase length ranges from 17°C to 30°C at C14 and C7 homologue, respectively. The mesomorphic transition temperature ranges are between 70°C and 113°C.

Mesomorphism and flexibility of alkyl chains in chalcone esters

ABSTRACTA novel homologous series of chalconyl ester liquid crystals (LCs): RO−C6H4–CH:CH–COO−C6H4–CO−CH:CH−C6H4–OC10H21 (n) (para) has been synthesized and studied with a view to understanding and establishing the relationship between molecular structure and LC properties with reference to flexibility of the terminal chain. The novel series consists of eleven homologs (C1–C16). The C1 and C2 homologs are nonliquid crystals and the rest of the homologs (C3–C16) are enantiotropic nematic without exhibition of smectic mesophase. Transition and melting temperatures were determined by an optical polarizing microscope equipped with a heating stage. Textures of nematic phases are threaded or Schlieren. Cr-N/I transition curve adopts a zigzag path in a normal manner with overall descending behaviors. The N-I transition curve exhibits a sharp and shorter odd-even effect from C3 to C6 and it diminishes from and beyond C6 for higher homologs of longer n-alkyl chain (R) in more or less or negligible deviating manner from normal descending tendency. Thermal stability for the nematic is 116.4°C and mesophase length ranges from 19°C to 67°C at the C3 and C12 homolog respectively. The LC properties of present novel series are compared with structurally similar analogous series to derive group efficiency order.

Study of mesomorphism and its relation to molecular structure through molecular rigidity and flexibility

ABSTRACTNovel liquid Crystalline (LC) substances of chalconyl ester derivatives from Vinyl aromatic carboxylic acids are synthesized and studied with a view to understanding and establishing the relation between molecular structure, RO-C6H4-CH=CH-COO-C6H4-CH=CH-CO-C6H4-F (para) and LC properties of the thermotropic variety. Homologous series consists of eleven members (C1 to C16). C1 and C2 members of novel series are nonliquid crystals (NLC) and the rest of the homologues (C3 to C16) are enantiotropic nematic with absence of smectic property throughout. Transition temperatures and textures of homologues were determined by an optical polarizing microscope (POM) equipped with a heating stage. Textures of nematic phase are threaded or Schlieren. The transition temperatures of novel homologues are relatively lower than the corresponding dimeric trans n-Alkoxy Cinnamic acids from which, novel homologues are synthesized. Thermal, analytical, spectral data confirmed molecular structures of novel homologues. Cr-N/I and N-I transition curves behaved in normal manner except C8 to C14 homologues which deviated from normal descending tendency in N-I transition curve. N-I transition curve exhibited odd-even effect up to C6 homologue and odd member's N-I transition curve occupied lower position than even member's N-I transition curve. Thermal stability for nematic is 118.2°C; with its total mesophase length ranging from 12.0 to 50.0°C. Thus, it is a middle ordered melting type series with absence of smectic property. Group efficiency order derived on the basis of thermal stability using comparative study of present novel series with structurally similar analogous series as mentioned below.Smectic: Series-Y > Series- X = Series-1 andNematic: Series-X > Series- 1 > Series-Y

Mesomorphism dependence on the combined effect of molecular rigidity and flexibility

ABSTRACTA novel liquid crystalline (LC) homologous series of azoesters with a laterally substituted methoxy group RO-C6H4-COO-C6H3-(-OCH3)-N═N-C6H4-COO-C4H9(n) has been synthesized and studied with a view to understanding the effect of molecular structure on thermotropic mesomorphism. The novel homologous series consists of thirteen homologues (C1–C18). The C1–C5 homologues are nonliquid crystals. The C6 and C7 homologues are only enantiotropically nematogenic and the rest of the mesomorphic homologues (C8–C18) are enantiotropically smectogenic and nematogenic. Transition temperatures and the textures of the mesophases were determined using an optical polarizing microscope (POM) equipped with a heating stage. The novel azoester homologues were characterised and confirmed using their analytical, spectral and thermometric data. Transition curves Cr-M/I, Sm-N and N-I behaved in normal manner without (Sm-N) and with (N-I) exhibition of odd-even effect respectively in a phase diagram. Thermal stabilities for smectic and nematic are 100.0°C and 127.7°C whose, mesomorphic phase length vary from 13.0°C to 24.0°C and 11.0°C to 33.0°C, respectively. The mesomorpism is compared with other known series.

Dependence of thermotropic mesomorphism on varying rigidity of central bridge in liquid crystals

ABSTRACTA novel liquid crystalline(LC) homologous series of chalconyl esters: RO-C6H4-COO-C6H4-CH = CH-CO-C6H4F has been synthesized and studied with a view to understanding and establishing the relationship between thermotropic LC properties and molecular structure with reference to varying molecular rigidity due to linking groups. The novel homologous series consists of eleven members (C1 to C16). C1 and C2 homologues are nonliquid crystals (NLC) and the rest of the homologues are enantiotropically nematic (C3 to C16). The smectogenic character, either in enantiotropic or monotropic manner is totally absent for a series. Transition temperatures and textures of nematic phase were determined by an optical polarizing microscope (POM) equipped with a heating stage. Textures of the nematic phase are threaded or Schlieren. The analytical, thermal and spectral data support the molecular structures. Cr-N/I and N-I transition curves behaved in normal manner except for the C14 homologue. N-I transition curve exhibits an odd- even effect with a negligible deviating effect from the C10 homologue. Thermal stability for the nematic is 105.2°C and mesophase lengths range from 06.0°C to 46.0°C at C8 and C14 homologues respectively. The group efficiency order derived for nematic from the comparative study of present novel series with structurally similar analogous series on the basis of thermal stability as under.

Dependence of thermotropic mesomorphism on lateral nitro group

ABSTRACTA 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).

Synthesis and mesomorphic behavior of liquid crystal chalconyl esters

ABSTRACTA chalconyl homologous novel series of thermotropic liquid crystals (LC) have been synthesized and studied with a view to understand and establish the effects of molecular structure on LC properties in thermotropic behaviors. Homologous series consists of 13 homologs (C1–C18), C1–C4 homologs are nonliquid crystals and the rest of the homologs are enantiotropically nematogenic without exhibition of smectic property. Transition temperatures and the textures of the nematic phase were determined by an optical polarizing microscopy, equipped with a heating stage (POM). Texture of a nematic phase are threaded or Schlieren. The Spectral and analytical data confirms the molecular structures of homologs. Cr-N/I and N-I transition curves behaved in normal manner except C7 homolog which shows negligible abnormality for N-I transition temperature or curve with exhibition of odd-even effect.

Dependence of mesomorphism on molecular rigidity of nonlinear and linear isomeric and nonisomeric chalconyl esters

ABSTRACTThe novel thermotropic liquid crystalline (LC) materials have been synthesized and studied through chalconyl ester nonlinear (meta substituted) homologous series RO-C6H4‒CH˭CH‒COO‒C6H4-CO‒CH˭CH‒C6H4-OC14H29(n) with a view to understand the effect of molecular structure on LC behavior with reference to determine the difference between linear and nonlinear shaped molecules. Novel series consisted of thirteen members, whose nematogenic enantiotropic mesomorphism commences from C6 homologue and continued up to C18 homologue with the absence of smectogenic character. C1 to C5 homologues are nonliquid crystals as determined through an optical polarising microscope (POM) equipped with a heating stage. Transition temperatures of LC homologues alternate and are lower than the corresponding n-alkoxy cinnamic acids. Cr-N/I and N-I transition curve behaved in normal manner. N-I transition curve exhibited odd-even effect in a phase diagram. Textures of nematic phase are threaded or Schlieren or determined by miscibility method and from observing mesophase on the top of the POM. Thermal stability for nematic is 92.5 and mesophase length minimum to maximum is 19.0 to 32.0°C at the C10/18and C6 homologue. Group efficiency order on the basis of thermal stability is Thus, novel series is nematogenic and low melting type. Analytical and spectral data confirmed the molecular structures of homologues.

Converting Nonliquid Crystals into Liquid Crystals by N-Methylation in the Central Linker of Triazine-Based Dendrimers.

Two triazine-based dendrimers were successfully prepared in 60-75% yields. These newly prepared dendrimers 2a and 2b containing the -NMe(CH2)2NMe- and the -NMe(CH2)4NMe- linkers between two G3 dendrons, respectively, exhibit columnar phases during the thermal process. However, the corresponding dendrimers 1a and 1b containing the -NH(CH2)2NH- and the -NH(CH2)4NH- linkers between two G3 dendrons, respectively, do not show any LC phases on thermal treatment. Computational investigations on molecular conformations reveal that N-methylation of the dendritic central linker leads dendrimers to possess more isomeric conformations and thus successfully converts non-LC dendrimers (1a and 1b) into LC dendrimers (2a and 2b).

Dependence of thermotropic mesomorphism on molecular flexibility of changing tail group

ABSTRACTA novel chalconyl ester homologous series of liquid crystals has been synthesized and studied with a view to understanding and establishing the effect of molecular structure on liquid crystalline properties. Novel series consisted of 13 members (C1–C18) of a series. C1–C4 member of a series is nonliquid crystals and, the rest of the homolog members (C5–C18) are enantiotropically nematogenic with absence of smectogenic property. None of the homolog is monotropically mesomorphic. Transition and melting temperatures were determined by an optical microscope equipped with a heating stage. Textures of nematic phase are threaded or schlieren. Spectral and analytical data of selected members of a series confirms the molecular structures of homologues. Cr-N and N-I transition curves of a phase diagram behaved in normal manner with exhibition of odd-even effect of very short range as observed for N-I transition curve. Thermal stability for nematic is 122.0°C and the nematogenic mesophase ranges from 7.0°C to 38.0°C. Liquid crystal properties of a present series are compared with the structurally similar known homologous series.

Mesomorphism dependence on tail group

ABSTRACTA chalconyl homologous novel series of thermotropic liquid crystals (LC) have been synthesized and studied with a view to understand and establish the effects of molecular structure on LC properties in thermotropic behaviors. Homologous series RO-C6H4-COO-C6H4-CO-CH=CH-C6H4-OC14H29 consists of 13 homologs (C1–C18), C1–C6 homologs are nonliquid crystals and the rest of the homologs are enantiotropically nematogenic without exhibition of smectic property. Transition temperatures and the textures of the nematic phase were determined by an optical polarizing microscopy, equipped with a heating stage. Texture of a nematic phase are threaded or schlieren. The Spectral and analytical data confirms the molecular structures of homologs. Thermal stability for nematic is 123.0°C and its mesogenicphaselength ranges between 13°C and 34°C. Cr-N/I and N-I transition curves behaved in normal manner except C14 homolog which shows negligible abnormality for N-I transition temperature or curve with exhibition of odd-even effect. Some LC properties are compared with the structurally similar homologous series. Thus, present homologous series is nematogenic and middle ordered melting type.

Mesomorphism dependence on molecular flexibility

ABSTRACTA novel ester homologous series of liquid crystals with a highly polar laterally substituted –OCH3 group is synthesized and studied with a view to understanding and establishing the effects of molecular structure involving lateral substitution on liquid crystal behavior. The novel series RO·C6H4·COO·C6H3·OCH3(ortho)CH=CH·COO·C2H5 consists of 12 homologs of which C7, C8, C10 are nematogenic and C12, C14, C16 homologs are smectogenic. The rest of the homologs are nonliquid crystals. The textures of nematic phase are threaded and the smectic phase is of the type A or C. Transition temperatures and the textures of mesophases were determined by an optical polarizing microscope equipped with a heating stage. Analytical and spectral data support the molecular structures. The N-I and Sm-I transition curves behave in normal manner without exhibition of an odd-even effect. Average thermal stability for smectic and nematic are 127.3°C and 129°C, respectively. The total mesophase length ranges from 17°C to 57°C and series is of a middle ordered melting type with transition temperatures varying between 82°C and 148°C. The liquid crystal properties of present novel series are compared with, structurally similar known homologous series.