Refractive Indices,calculated orientational order Parameters,and Polarizability Anisotropies of Liquid Crystalline 3-(4-Alkyl-phenyloxy)-propane-1,2-diols

For a novel variant of smectic structures the S_A⁺ phase of the homologous 3-(4-alkyl-phenyloxy)-propane-1,2-diols the refractive indices n_e and n_o were measured in dependence on the temperatue. The polarizability anisotropy, the orientational order parameter, and the packing fraction were calculated using a mean field fitting method. The components of the internal field tensor were included in the fitting procedure. The increasing mobility of the alkyl chain for higher homologues reduces the orientational order in the smectic layers and also the birefringence which is very small. The molecular polarizabilities are increasing nearly linearly with the elongation of the alkyl chain. The small alternation of the polarizabilities corresponds to the alternating change of the length-to-breadth ratio. The calculated packing fractions are enhanced for higher homologues.     

Dynamic Scattering with Storage in Smectics C and Nematics with Smectic C Ordering

Stored dynamic scattering and stored domain structure were observed in smectic C and in nematic phases of p-n-heptyloxybenzoic acid (HOBA). The sdtored texture can easily be erased with a high frequency electric field. The smallest frequency for erasure decreases with the decreasing temperature. Stored scattering centers and stored domain structure in S₁ solid phase of HOBA were also observed.     

Calorimetric Study of Crystalline and Liquid-Crystalline Polymorphism in the Homologues of Terephthal-bis-n-alkylaniline

The phase sequences of the homologues with n (the number of carbon atoms in the terminal alkyl chains) from 2 to 8 are obtained. At low temperatures, i) several crystalline modifications are found in each of the members with n = 4, 5, and 6 and ii) the monotropic transitions between crystal and smectic phase are observed in almost all the members. At intermediate temperature, iii) between the smectic H and C phases, the smectic F phase is found in the homologues with n ≥ = 5 by morphological observation or by a rheological method. The constancy of the temperature of the S_H(or S_F) – S_c transition with respect to “and broadening of the temperature range of S_H with increasing n in the expense of nematic phase are worthy of note. The even-odd effect of the end chain length n is observed very distinctively on the crystal melting and clearing point. Proton NMR measurement reveals a large mobility in the terminal alkyl chains in the crystal of the member with n = 6.     

Refractive Indices and Dielectric Studies of Three Phenylcyclohexane Liquid Crystals in the Nematic Phase

The refractive indices n_e, n_o and densities and the dielectric primittivities ε_∥ and ε_⊥ of three P-cyano-P-alkylcyclohexanes (PHC-3, PCH-5, PCH-7) have been measured at different temperatures. The order parameters calculated by using Neugebauer and Vuks' methods were comparable. A comparison of order parameters of the PCH with the corresponding alkylcyanobiphenyls at reduced temperatures τ (= T-T_NI/T_NI) shows that the replacement of a phenyl ring with a cyclohexyl ring decreases the order parameter appreciably. The experimental values of dielectric permittivities ε_⊥ in each of the PCHs are found to be less than half of the ε_⊥-value calculated from Maier and Meier equations using the polarizability and the order parameter obtained from refactive index measurements. This was explained as due to short range antiparallel ordering of strongly polar molecules in the nematic phase, as proposed by Chandrasekhar and Madhusudan, which was not taken into consideration in Maier and Meiers' theory     

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.     

High Pressure Studies on Partially Bilayer and Monolayer Smectics

We have carried out pressure studies on the eighth and ninth members of the homologous series 4-alkoxybenzoyloxy-4′-cyanoazobenzene (nOBCAB). It is found that the pressure behavior of the monolayer smectic A (A₁) phase is entirely different from that of the partially bilayer smectic A (A₁) phase. The A₁ -nematic phase boundary is a straight line at all pressures and the range of the A_d phase increases with increasing pressure. On the other hand, the A_d -nematic phase boundary is elliptic in shape and the A_d phase gets bounded. These results emphasize the fact that the pressure behavior of the A phase is strongly related to the extent of overlap of the molecules in the layer.     

Heat Capacity and Thermodynamic Properties of p'-Substituted p-n-Hexyloxybenzylideneaniline I I I. p-n-Hexyloxybenzyl ideneam i no-p'-fluorobenzene (HBAF)

Abstract

The heat capacity of HBAF has been measured between 15 K and 385 K. Four phase transitions were found at 328.07 K (crystal-smectic B); 330.33 K (smectic B-smectic A); 334.88 K (smectic A-nematic); and 336.33 K (nematic-isotropic liquid), respectively. The enthalpies and entropies of these transitions were determined to be 23.22 kJ mol^?1/70.7 JK^?1 mol^?1; 3.05/9.2; 3.41/10.2; and 1.17/3.5, respectively. The total transition entropy of HBAF agreed well with those previously reported for the present homologues. The standard thermodynamic functions were estimated up to 385 K. The heat capacity curve of HBAF in the transition region had a close resemblance to that of p-n-hexyloxybenzylideneamino-p'-chlorobenzene. The entropies of the smectic A-nematic and nematicisotropic liquid transitions were compared with those theoretically derived by McMillan. The smectic B-smectic A transition entropy was interpreted in terms of order-disorder phase transition associated with the orientation of molecule.     

Mesomorphism dependence on molecular rigidity with reference to ‒CH˭CH‒ unit of central bridge

A novel ester homologous series of rich mesomorphism and low temperatures with unexpected phase behaviors of eleven homologues was synthesized and studied with a view to understanding and establishing the relation between mesomorphic behaviour and the molecular structure of a series 4-(4′-n-alkoxybenzoyloxy)-4″-chlorobenzyl cinnamates. All the members of the novel series are enantiotropically smectogenic and the octyloxy (C₈) to hexadecyloxy (C₁₆) homologues are enantiotropically nematogenic, in addition to smectogenic. Odd–even effect is observed for Sm?I/Sm?N transition curve but it is absent for N?I transition curve. Textures of nematic phase are threaded or Schlieren and that of the smectic phase are fan shaped or batonates of smectic-A type phase or Smectic-C type for C₁₆ homologues as judged directly from a heating stage of an optical polarizing microscopy. Analytical and spectral data confirmed the molecular structures of novel homologues. Mesomorphic properties of present series are compared with the structurally similar other known series. The average smectic and nematic thermal stabilities are 92.78°C and 100.8°C, respectively. Mesophase length minimum to maximum for smectic and nematic are 21.0°C to 31.1°C and 8.4°C to 42.6°C respectively. Thus, the present novel series is partly nematogenic and fully smectogenic with considerable degree of mesomorphism and low melting type.     

Some New Smectic F Materials

In the course of studies on the smectic C phase, we have succeeded in preparing three new compounds each of which exhibits a well defined smectic F phase. In all of these materials, the F phase gives a smectic C phase on heating and a smectic H phase on cooling. Moreover, these three compounds are members of two related homologous series of esters; therefore it seems probable that many more of the other homologues will exhibit smectic F properties.     

Dispersive power and crossover temperature,TCO, of two polar nematic liquid crystals in the visible spectral region

Refractive index studies are carried out on two highly polar liquid crystals: 1. N-(p-n-methoxy benzylidene)-p-amino benzonitrile, PmBAB, 2. N-(p-n-ethoxy benzylidene)-p-amino benzonitrile, PeBAB. The experimental investigations are carried out in the visible region at four different wavelengths, namely, 633, 589, 546 and 436 nm. The two compounds exhibit only the nematic liquid crystalline phase in between the isotropic and crystalline solid. The dispersive power ω is estimated for two consecutive wavelengths for the case of <n>, n_e and n_o for different wavelengths and found to be constant with temperature. Further the temperature gradients of n_e and n_o are estimated, and the crossover temperature is obtained using dn_o/dT for all the wavelengths.     

Dielectric Anisotropy and the Order Parameter of HXBBA

Abstract

Measurements of dielectric anisotropy (Δ?), refractive indices (n _e , n _o), birefringence (Δn) and density (ρ) have been made in the nematic and smectic phases of N(-p-hexyloxybenzylidene)-p-butylaniline (HXBBA). The results indicate that the various transitions are of the first order type except smectic B-smectic G, which may be a second order transition. The order parameter S has been determined using the isotropic internal field model (Vuks approach) and the anisotropic internal field model (Neugebauer's approach) and both the values agree fairly well. The dielectric anisotropy (Δ?) increases strongly in the smectic phases whle S increases only slowly. It is interpreted by an increase of dipole-dipole correlations.     

Biphenylbenzoates: Synthesis and Thermodynamic Properties

Two homologous series of twelve compounds each of biphenylbenzoates have been synthesised and their mesomorphic properties characterised. Heats of transition for both series of compounds have also been measured using differential scanning calorimetry. In the biphenyl 4-p-n-alkoxybenzoate series the first few members are monotropic nematic and the higher ones exhibit enantiotropic nematic as well as smectic phases, whereas in the biphenyl 4-p-n-alkyl benzoate series only the monotropic nematic phase is observed. In both series of compounds the plot of the nematic-isotropic transition temperature against the number of carbon atoms in the alkyl chain exhibit smooth curve relationships.     

Elasticity and Orientational Order in Some trans-p-n-Alkoxy-α-methyl Cyanophenyl Cinnamates

The splay (k ₁₁), twist (k ₂₂) and bend (k ₃₃) elastic constants determined by the Freedericksz method and the orientational order parameters (s) derived from optical measurements in the nematic phase of six homologues of trans-p-n-alkoxy-α-methyl cyanophenyl cinnamates (n OMCPC) are reported. The data close to the nematic-isotropic transition point (T _NI) are compared with T _NI and the heats of transition (ΔH). The temperature-variation of elastic constants is discussed in terms of existing theories. The pretransitional increase in the twist and bend constants near the nematic-smectic A transition point (T _NA ) of 10 OMCPC has also been analysed.     

Dielectric Studies of Three Liquid Crystals HBT,E8 and PCH-1132

The dielectric behavior of a Schiff base N-(P-Hexyloxybenzylidene)-P-toluidine (HBT) and two technologically important mixtures, E₈ and PCH-1132, are reported in the radio frequency region. The value of the mean dielectric constant increases by ～5% on going from the nematic to the isotropic phase in the case of E₈ and PCH-1132. This may perhaps be due to antiferroelectric arrangement of the molecules in the nematic phase. These mesogens show unusual dielectric behavior and exhibit positive anisotropy at lower frequencies and negative dielectric anisotropy above a critical frequency termed as isotropic frequency. The isotropic frequency is found to be temperature dependent. All these nematogens exhibit single relaxation in the radio frequency region which is due to hindered rotation of the molecules under nematic potential. The relaxation frequencies are 3.98 MHz (at 61.4°C), 2.27 MHz (at 34.3°C), 1.87 MHz (at 33°C) in case of HBT, E₈ and PCH-1132 respectively. The activation energy is found to be 16.7 KCal/mole, 14.6 KCal/mole and 16.1 KCal/mole for HBT, Ea and PCH-1132 respectively. In smectic B phase of HBT, the dipolar orientations are found to be somewhat “locked” similar to that in solids. The inversion of the sign of dielectric anisotropy in S_B phase of HBT is also discussed.     

Dielectric constant,loss factor and ac conductivity of Ni2+‐doped K2ZnCl4 crystals in the ferroelectric‐commensurate,incommensurate and normal phases

The dielectric constant (ϵ), dielectric loss (tanδ) and ac conductivity (σ_ac) of virgin and thermally cycled undoped and Ni²⁺‐doped K₂ZnCl₄ (KZC) crystals in the ferroelectric‐commensurate (FC), incommensurate (IC) and normal phases (N) have been studied. Anomalous behaviour at the two‐phase transition points was observed while measuring ϵ along the polar a‐axis for the undoped sample. With increasing Ni²⁺concentration a systematic shift of the phase transition temperature towards lower values and a continuous inhibition of the peak height were detected. ϵ changed linearly with lnf up to f =10⁵ Hz. tanδ along the a‐axis declared the phase transitions by peak changes. After Ni²⁺‐doping this behaviour was preserved at the FC‐IC phase transition point while the IC‐N phase transition was manifested by a change in the slope of the straight line representing the tanδ‐T dependence. The ac conductivity changed lineally with frequency according to a relation of the form σ_ac = σ_o f ^β where 0>β>1.9. σ_ac increased monotonically with increasing temperature and doping concentration in the low‐temperature phases tending to merge in one straight‐line with high activation energy that might be due to superionic dc conduction in the high temperature N‐phase. Doping with Ni²⁺ pinned stripples, decreased the soliton‐soliton interaction, weakened discommensuration effects, shortened the IC‐phase and strongly affected the ‘chaotic' behaviour at the T_C‐IC. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Effect of polarity of smectic Ad molecules on the induction of the nematic phase in binary mixtures of smectics A1 and Ad

The phase diagrams are determined of binary mixtures composed of 4-n-alkylbiphenylates 4-cyanobiphenyl (n-CBB)-smectics A₁, for n < 8 and esters of 4-(trans-4′-n-alkylcyclohexyl)benzoic acid (10CPCHB, 10NPCHB, 10FOPCHB)-smectics A_d. The effect is studied of the smectic layer spacing ratio and polarity of the components on the induction of the nematic phase in the tested series of compounds. The virtual N S_Ad phase transition points in series n-CBB are estimated and the effect is discussed of the stability of the smectic phase and polarity of the molecules of the mixture components on the width and position of the nematic gap.     

Smectic C-to-Nematic Transition in p-n-Heptyloxybenzylidene-p-aminobenzoic Acid

The results on the phase transitions in p-n-heptyloxybenzylidene-p-aminobenzoic acid are reported. The microscopic and X-ray studies show that the compound goes over from smectic C to nematic phase directly. The transition entropies and specific heat are determined using differential scanning calorimetry. The translational order parameter is determined using low angle X-ray intensity measurements. The tilt angle in smectic C phase is found to be 56° and is independent of temperature. The X-ray data also lead to the conclusion that the compound exists as a dimer.     

Mesomorphism Dependence of Molecular Flexibility with Reference to Bromo Tail Group

Halogenated chalconyl derivatives of novel homologues of esters are synthesized and studied with a view to evaluate their liquid crystal (LC) properties and their dependence on molecular structure with reference to molecular rigidity and flexibility. Novel homologous series of chalconyl esters comprises 12 homologues. All the members of a series are enantiotropically smectogenic. Nematogenic mesophase is missing throughout the series. Textures of smectic phase are of type A or C, as judged either by observing directly the sample homologue through polarizing microscopy or some selected members of the series by miscibility method. Transition temperatures were observed through an optical polarizing microscope equipped with a heating stage. The Cr-Sm transition curve adopts zigzag path and behaves in a normal manner. Sm-I transition curve exhibits an odd-even effect and behaves in a usual established manner. The average thermal stability for smectic is 154.79°C, and the mesogenic phase length range is from 5.1 to 24.4°C. The LC properties of the novel series are compared with structurally similar other known series. Thus, present novel series is fully smectogenic with middle ordered melting type and short range of liquid crystallinity.