Thermal and optical studies on induced smectic phases of inter molecular hydrogen bonded liquid crystals between decyloxy benzoic acid and citric acid

Hydrogen bonded liquid crystal complex (HBLC) is prepared from mesogenic 4-decyloxy benzoic acid (10OBA) and aliphatic nonmesogenic citric acid (CA). Liquid crystal (LC) phases are investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) studies. Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (NMR) validate the intermolecular complementary, cyclic type of hydrogen bond (HB) and molecular environment in the designed HBLC complex. Mesomorphic phases like nematic, smectic X (Sm X) and smectic G (Sm G) are characterized by various textures and using different techniques such as POM, DSC and optical tilt angle measurements. Thermal span width and thermal stability factor for the observed phase is calculated. The complexes are prepared in different mole ratio and their corresponding influences on the phase transitions are discussed. Also it is observed that the HB units play a vital role in stabilizing the new Sm X phase. The variation in thermal stability of smectic phases due to the influence of aromatic cores and length of end chain in the different mole ratio of the present HBLC complexes are also discussed. The variation of tilt angle with respect to temperature in the smectic phase has been experimentally calculated and analyzed. The lowered melting and clearing transition temperatures and extended thermal span width in the Sm X phase are also reported.     

Characterisation and mesomorphic behaviour of liquid crystals with dispersed PdCl2 nanoparticles

The synthesis and characterisation are carried on liquid crystalline (LC) p-dodecyloxy benzoic acid (12OBA) with 1 and 2 wt% for PdCl₂ nanoparticles dispersion. Further, characterizations are carried out by different spectroscopic techniques like X-ray diffraction spectrometric studies, scanning electron microscopy, Fourier transform infrared and differential scanning calorimetry (DSC). Textural determinations of the synthesised compounds are recorded by using polarising optical microscope (POM) attached with a hot stage and camera. The results show that the dispersion of PdCl₂ nanoparticles in 12OBA exhibits Nematic phases as same as the pure 12OBA with reduced clearing temperature as expected. Further, the nematic thermal ranges are quenched and the smectic C thermal range has been increased while performing both DSC and POM with the dispersion of 1 wt% PdCl₂ nanoparticles. Size dependence on bonding nature with LC compounds is established.     

Diaquabis(5-methoxyindole-2-carboxylato)bis(3-picoline)nickel(II) Complex: Synthesis,Characterization, XRD,TGA, DFT and HSA

A new complex of diaquabis(5-methoxyindole-2-carboxylato)bis(3-picoline)nickel(II) (Ni(5-MeOI2CA)₂(3-pic)₂(H₂O)₂), was synthesized for the first time and characterized by elemental analysis, FT-IR and electronic spectroscopy (UV-Vis) and single-crystal X-ray diffraction (XRD) techniques. The thermal degradation of the Ni(II) complex was investigated using thermogravimetric and differential thermal analyses techniques in oxygen atmosphere. The molecular structure of the complex was determined by single crystal X-ray diffraction technique. Hirshfeld surface analysis (HSA) investigated the packing modes and intermolecular interactions in molecular crystals, as they provide a visual picture of intermolecular interactions. In addition, all computational studies at B3LYP/6-311++G(d,p) were carried out for theoretical characterization of Ni(II) complex. The optimized geometry results, which were well represented the X-ray data, were shown that the chosen of DFT/B3LYP/6-311++G(d,p) was a successful choice for title compound. After a successful optimization, FMOs, chemical activity, non-linear optical properties (NLO), molecular electrostatic potential (MEP), Mulliken population (MPA), natural population analyses (NPA), Fukui function analysis (FFA) and natural bond orbital analysis (NBO), which could not obtained by experimental ways, were calculated and investigated. The computed of net charges and chemical activity studies which helped to identifying the electrophilic/nucleophilic nature.     

Linear Double Hydrogen-bonded Thermotropic Liquid Crystals Formed Between Oxaloacetic Acid and p-n- Alkyloxy Benzoic Acids

Double hydrogen-bonded thermotropic liquid crystal complexes (DHBLC) have been isolated from molar ratios of Oxaloacetic acid (OAC) and eight alkyloxy benzoic acids (nBAO) whose carbon number varied from pentyloxy to dodecyloxy. The complexes are referred as OAC+nBAO where n varied from 5 to 12. In each of the synthesized complexes, complementary hydrogen bonds formed are confirmed by FTIR study and the complexes are further investigated by Polarizing Optical Microscopy (POM), Differential Scanning Calorimetry (DSC) for the construction of phase diagram. Characteristic phases like nematic, smectic C, smectic F, and smectic G are characterized by various textures. From DSC studies, odd–even effect is evinced in transition temperatures across isotropic to nematic phase transition and across smectic F to smectic G phase transition in enthalpy values. The order of all transitions observed in eight complexes is calculated by thermal analysis. The magnitude of optical tilt angle in smectic C is fitted to a power law and the scale of critical exponent is found to concur with the Mean Field theory predicted value.     

Density Studies in Polymorphic Liquid Crystal N- (p-n-Heptyloxybenzylidene) p-n-Pentylaniline

Density studies in polymorphic liquid crystal, N-(p-n-heptyloxybenzylidene) p-n-pentyl-aniline is carried out in isotropic liquid, nematic, smectic A, smectic C, smectic B and smectic G phases. The temperature variation of density in all the mesophases confirms that isotropic liquid to nematic, nematic to smectic A, smectic C to smectic B, smectic B to smectic G transitions are of first order while smectic A to smectic C transition is of second order. The density variation across smectic C to smectic B is greater than that of any other transition. Thermal expansion coefficients are also calculated.     

Mesomorphism dependence on lateral substitution of functional groups and their position in series: 4(4′-n-alkoxy benzoyloxy)-3-chloro phenyl azo-2″-methoxy benzenes

Eleven homologues of the title series were synthesized. The methyl-to-pentyl derivatives are nonmesomorphic. The nematic mesophase commences from the sixth member of the series without any smectic phase. An odd–even effect in the nematic–isotropic transition curve is not observed. The nematic mesophase appeared as a threaded or a Schlieren-type texture as observed through a hot-stage polarizing microscope. The nematic–isotropic transition temperatures are between 89°C and 127°C with the mesomorphic range varying from 9°C to 44°C at the hexyl and tetradecyl derivative of the series, respectively. The nematic–isotropic transition curve initially rises and then falls in a normal manner as the series is ascended, but it abnormally rises beyond the 10th homologue. The series is enantiotropic nematic with a middle-ordered melting type. Analytical data support the structures of the molecules. The thermal stability and some other mesomorphic characteristics are compared with structurally similar homologous series. The average nematic–isotropic thermal stability is 105.4°C.     

Study of the Effect of Lateral Substitution on Mesogenic Behavior with Reference to -CH=CH- Unit

A novel cinnamate ester homologous series has been synthesized and studied with a view to understanding and establishing the effects of molecular structure on liquid crystal (LC) properties with a focus on the highly polar methoxy group as a lateral substituent. The series consists of twelve homologs; of which C₁–C₅ are nonmesogenic, and the rest of the homologs are enantiotropically smectogenic or and nematogenic. The texture of nematic phases is threaded or Schlieren and that of the smectic is either smectic A or C, as recognized and determined through an optical polarizing microscope equipped with a heating stage. The Sm-N I and N-I transition curves exhibit odd-even effects and behave in normal manner. The Cr-I M behaves in normal manner. Analytical and spectral data confirm the molecular structures of homologs. The average thermal stabilities for smectic and nematic are 125.3 C and 129.8 C, respectively, whose total mesophase length varies from 13 C to 51 C. Some LC properties of present series are compared with the structurally similar known series.     

Phase transition studies in mesogenic dimers

Schiff base liquid crystal dimers, both symmetric and non‐symmetric, in which two anisotropic groups are linked by a flexible spacer, exhibit a rich variety of smectic mesomorphism. The interest in this class of mesogens stems not only from their ability to act as model compounds for semi‐flexible mainchain liquid crystal polymers but also from their quite different properties compared to conventional low molar mass liquid crystals (monomers). We report here the phase transition studies on two examples of these schiff base liquid crystal dimers using the Differential Scanning Calorimetry and density measurements as a function of temperature. The symmetric liquid crystal dimer, α,ω‐bis (4‐n‐dodecylaniline benzylidene‐4′‐oxy)decane (10.O12O.10) exhibits a very rare Isotropic to G transition. Where as, the non‐symmetric dimer, α‐(4‐cyano biphenyl‐4′‐yloxy)‐ω‐(4‐n‐decylanilinebenzylidene‐4′‐oxy)decane (CB.O10O.10) exhibits a rare nematic to intercalated smectic A phase transition. The transitions studied, isotropic to nematic and isotropic to G exhibit a large density jump at the transition confirming their first order nature. Nematic to intercalated smectic A transition is found to be a second order transition whose behavior is similar to nematic to smectic A transition. Calculated values of pressure dependence of transition temperature and thermal expansion coefficient are also reported.     

Mesomorphism dependence on central bridge (-COO-CH2-) and terminal end group (-Br)

A novel series of liquid crystalline (LC) ester materials has been synthesized and studied with a view to understanding the effects of molecular structure on LC behavior. The homologous series of eleven members is entirely enantiotropically smectogenic without exhibition of a nematic phase. Transition temperatures and the texture of smectic phase was determined by an optical polarizing microscope equipped with a heating stage (POM). Transition curves (Cr-Sm and Sm-I) showing phase behavior in a phase diagram behave in a normal manner. Textures of smectic phase are focal conic fan shaped of the type Smectic-A or Smectic-C. An odd–even effect is exhibited by the Sm-I transition curve. The average thermal stability for smectic is 91.2°C and the mesogenic phase length ranges between 3.6°C and 39.3°C. Thus, the novel smectogenic homologous series is a middle-ordered melting type whose LC phase is relatively middle ordered. The LC properties of the present series are compared with a structurally similar homologous series. Analytical and spectral data support the molecular structures.     

Density and Ultrasonic Velocity Measurements in Hexyloxybenzylidene Phenylazoaniline

The temperature variation of density and ultrasonic velocity of the liquid crystal hexyloxybenzylidene phenylazoaniline are reported. The density across the smectic A—smectic B transition is more predominant than the other transitions. The density variation with temperature and the calculated thermal expansion coefficients suggest that the transitions isotropic liquid—nematic, nematic—smectic A and smectic A—smectic B are of first order. Anomalous behaviour of ultrasonic velocity is observed across the isotropic liquid—nematic transition and prominent dips in velocity are observed at the nematic—smectic A and smectic A—smectic B transitions. The adiabatic compressibility (β _ad ) Rao number (R _a ) and molar compressibility (B) are estimated using the experimental density and ultrasonic velocity.     

Complex zigzag flexoelectric walls in the Schlieren textures of MBBA: possibility for determination of two basic Schlieren textures with singular or non‐singular surface points

The flexo‐dielectric behaviour of a homeotropic MBBA nematic layer has been experimentally studied. Asymmetric strong‐weak anchoring of the homeotropic nematic layer was achieved by treating the glass plates – one of them with lecithin ensuring the strong anchoring and the other with usual soap ensuring the weak anchoring. The application of a dc voltage with a sufficient amplitude led to the appearance of a complex texture consisting of gradient flexo‐dielectric deformations including Schlieren texture with many singular points and zigzag flexoelectric walls. The application of additional orienting a.c. voltage brought clarification of the Schlieren texture resembling that of the smectic‐C liquid crystal. Inversely, the application of an ac voltage across the homeotropic nematic layer led to formation of a nice Schlieren texture. The additional application of a d.c. voltage created complex zigzag gradient flexoelectric walls which connected the singular points in the Schlieren texture. In this way, one can determine for the first time how many points in the initial Schlieren texture are singular and how many points are non‐singular. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mesomorphic Properties of Di- (4 - Alkoxyphenyl) and Di- (4 - Alkanoyloxyphenyl) Tetrathiafulvalenes

The polymorphism of the di- (4 - alkoxyphenyl) and di- (4 - alkanoyloxyphenyl) tetrathiafulvalenes (TTF) is investigated. In the dialkoxy series, the short chain derivative exhibits a smectic G phase and a nematic phase. The latter phase disappears in the long chain derivative. The dialkanoyloxy derivatives exhibit a smectic G phase (for short chains) and a smectic C phase (for long chains). A plot of the mesormorphic-isotropic transition temperatures against the number of carbon atoms of the substituent shows the usual odd-even effect. Some tetra (alkoxyphenyl) tetrathiafulvalenes are described, unfortunately they have no mesomorphic properties.     

Mesomorphic Properties of an Homologous Series of Alkoxy-Terminated Enamine-Ketone Containing Liquid Crystals

An homologous series of enamine-ketone compounds has been synthesized and their thermal properties investigated. The bis [3- p-n-alkoxyanilino)-2-butenoyl] benzenes exhibited nematic mesophases when the terminal alkoxy substituents were short and both nematic and smectic mesophases when the terminal alkoxy substituents contained twelve or more carbons. The thermal data indicate that although crystalline order is largely determined by the packing of the hydrocarbon tails, there is a low degree of interaction by the tails in the nematic mesophase.     

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.     

Thermal Microscopy and DSC Studies of 4-[4-n-pentyloxybenzylideneamino] Azobenzene

Phase transition studies of the liquid crystal, 4-[4-n-pentyloxybenzylidene–amino]–azobenzene (PBAAB) have been investigated by thermal microscopy and Differential Scanning Calorimetry (DSC) studies. From these studies it is confirmed that the compound, PBAAB exhibits nematic, smectic A and smectic B phases. The textures exhibited by different phases are presented. The enthalpies and entropies at various phase transitions are also reported.     

Phase transition studies of the liquid crystal 4-[4-n-hexyloxybenzylidene amino] azobenzene thermal microscopy and DSC

The phase transition temperatures of the liquid crystal 4-[4-n-hexyloxybenzylideneamino]-azobenzene have been investigated by the thermal microscopy and the Differential Scanning Calorimetric (DSC) studies. These studies confirm that this mesogen exhibits nematic, smectic A and smectic B phases. The transition enthalpies, transition entropies and also the textures exhibited by the different phases are presented.     

Phase Transition and Optical Characterization of Mesophase Stability of Nematic and Columnar Biphasic Regions

We report the results of our studies on the optical and thermal properties of binary mixture of two compounds viz., abietic acid and alizarin dye. The mixture shows a very interesting co-existent biphasic regions of nematic (N + I) and columnar smectic (C + I) phases, sequentially when the specimen is cooled from its isotropic phase respectively at different concentrations of given molecule. The temperature variations of optical anisotropy, optical textures and electrical conductivity have also been discussed. Aggregated molecular size has been confirmed by X-ray studies.     

The Polymorphism of 5-n-Hexyl-2-[4-n-pentyloxyphenyl]-pyridine

The phase transitions of 5-n-hexyl-2-[4-n-pentyloxyphenyl]-pyridine were determined by miroscopic and calorimetric investigations. The classification of the smectic modifications was done by investigation of the miscibility relations. Besides the nematic phase smectic phases C, F, G and H were identified.     

The Smectic A-Smectic A Transition in a Homologous Series of 4-(4-Alkoxyphenoxycarbonyl)phenyl 5-Cyano-2-furancarboxylates

The thermal properties for a homologous series of 4-(4-alkoxyphenoxycarbonyl)phenyl 5-cyano-2-furancarboxylates have been examined. The smectic A phase commences from the hexyloxy homolog, and the octyloxy, nonyloxy and decyloxy homologs show two kinds of smectic A phases and experience the S_A-S_A transition. The lower phase which shows a typical fan shaped texture is assigned to a smectic A with a bilayer arrangement of the molecules (S_A2). The higher phase which shows a typical fan shaped texture on the cooling stage and a broken fan one on the heating stage, is assigned to a smectic A with a partially bilayer arrangement of the molecules (S_Ad). The S_A-S_A transitions could be easily detected by both differential scanning calorimeter and optical microscopic method.