Phase Transition and Structural Investigations in 50.5, 50.6 and 50.7

Abstract

We report X-ray diffraction, density, ultrasonic velocity and refractive index studies in the N(p-n-pentyloxy benzylidene) p-n-alkylaniline compounds, viz. 50.5, 50.6 and 50.7. The nematic-smectic A (NA) transition is found to be weak first order in 50.6 while it is second order in 50.5 and 50.7. The salient features observed are cybotactic clusters in the nematic phase in all the compounds, molecular tilt which was inferred due to the end alkyl chains tilt causing orienta-tional disorder (smaller orientational order parameters ‘s’ than expected) in smectic A phase, smectic F phase and large tilt angle variation in smectic C phase in a small temperature range in 50.5. The observed results are discussed in the light of available data in other n0.m compounds.     

A detailed study of hydrogen bonded ferroelectric mesogens formed between alkyl and alkyloxy benzoic acids with carbamyl glutamic acid

A new ferroelectric homologous series of hydrogen-bonded ferroelectric liquid crystals is designed and synthesised with 14 compounds comprising two homologous series. The hydrogen bond is formed between dicarboxylic acid, viz. Carbamyl glutamic acid (CGA) with p-n-alkyl/alkyloxy benzoic acids (BA/BAO) and is confirmed by Fourier Transform Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR) studies. These two series referred as the CGA+nBAO and the CGA+nBA yields 14 mesogenic homologues and the mesogenic nature is detected by optical textures through polarising microscope which is confirmed through Differential Scanning Calorimetry (DSC). CGA+nBAO series exhibit cholesteric, smectic X*, smectic C* and smectic G* phases while CGA+nBA exhibits cholesteric and smectic G*phases. The enthalpy values of the corresponding temperatures are elucidated. Odd–even effect is evinced at smectic C* to smectic G* phase transition temperatures of CGA+nBAO series. The order of the individual phase transition and thermal stability factor of the phases is also calculated. Optical tilt angle in smectic C* phase is obtained by optical extinction method. Dielectric relaxation and their corresponding frequency shift observed in different ferroelectric phases are measured and a dielectric molecular modelling is presented. Crystallisation kinetic study of smectic G* phase in CGA+nBAO is computed. An interesting phenomenon – ‘Parachromatism’ – is elaborated.     

Nature of smectic A*-C* phase transitions in a series of ferroelectric liquid crystals with little smectic layer shrinkage

The smectic layer spacing of two homologous series of ferroelectric liquid crystal compounds was characterized by small-angle x-ray diffraction and different degrees of smectic layer shrinkage on cooling from the SmA* into the SmC* phase were observed. The smectic A*-smectic C* phase transition was further studied by measuring the thermal and electric field effects on the optical tilt angle and the electric polarization. With decreasing length of the alkyl terminal chain the phase transition changes from tricritical exhibiting high layer shrinkage to a pure second-order transition with almost no layer shrinkage. This is explained by the increased one-dimensional translational order of the smectic layers, which seems to promote the "de Vries"-type [Mol. Cryst. Liq. Cryst. 41, 27 (1977)] smectic A*-C* phase transition with no or little layer shrinkage.     

On the origin of high optical director tilt in a partially fluorinated orthoconic antiferroelectric liquid crystal mixture

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A* (SmA*) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C* (SmC*) and smectic C_a* (SmC_a*) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA* phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC* phase, the distribution is biased such that the molecular tilt already present in SmA* now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmC_a* is about 20° larger than in SmA*. The large optical tilt (45°) in the SmC_a* phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations.     

Direct smectic A-smectic C*A phase transition

The anticlinic smectic CA phase belongs to the class of tilted smectic phases with an azimuthal angle alternating from one direction (theta=0) to the other (theta=pi) in successive layers. It occurs in general at lower temperature than the uniformly tilted smectic C phase, but may be obtained directly from the untilted smectic A phase. We use the chiral nCTBB9* series synthesized in this laboratory, in order to obtain a phase transition as close as possible to second order, as revealed by DSC. We measure the temperature behaviour of the birefringence and of the optical rotatory power across the transition in order to characterize the tilt angle. We finally study the optical response to a periodic electric field which excites separately the smectic C* and C*A soft modes. The main conclusion is that the only order parameter governing the critica Al behaviour of the phase transition is the tilt angle theta, as we get common divergence of both soft modes at the same temperature. This confirms previous high resolution calorimetric studies by Ema et al. that saw in MHPOBC an initial mean-field second order phase transition when the tilt appears, followed by sharp first order restructuring transitions between the tilted subphases.     

Direct smectic A-smectic C*A phase transition

The anticlinic smectic CA phase belongs to the class of tilted smectic phases with an azimuthal angle alternating from one direction (theta=0) to the other (theta=pi) in successive layers. It occurs in general at lower temperature than the uniformly tilted smectic C phase, but may be obtained directly from the untilted smectic A phase. We use the chiral nCTBB9* series synthesized in this laboratory, in order to obtain a phase transition as close as possible to second order, as revealed by DSC. We measure the temperature behaviour of the birefringence and of the optical rotatory power across the transition in order to characterize the tilt angle. We finally study the optical response to a periodic electric field which excites separately the smectic C* and C*A soft modes. The main conclusion is that the only order parameter governing the critica Al behaviour of the phase transition is the tilt angle theta, as we get common divergence of both soft modes at the same temperature. This confirms previous high resolution calorimetric studies by Ema et al. that saw in MHPOBC an initial mean-field second order phase transition when the tilt appears, followed by sharp first order restructuring transitions between the tilted subphases.     

Electroclinic effect in the chiral smectic A and cholesteric phases at the proximity of a N*–SmA–SmC* multicritical point

We studied the electro-optic and dielectric properties of three pure ferroelectric liquid crystal materials (C10, C11 and C12) of the same series exhibiting cholesteric (N*), smectic A (SmA) and chiral smectic C (SmC*) phases. From electro-optic investigations, the tilt angle and spontaneous polarisation were determined as a function of temperature. In the dielectric measurements carried out without a dc bias field, we studied the soft-mode relaxation in the SmA phase. From experimental data and using the results of a Landau model, we evaluated the soft-mode rotational viscosity and the electroclinic coefficient in the SmA phase. A soft-mode like mechanism was also observed in the N* phase for compounds with shorter chains (C10 and C11). This relaxation process is not detected for the homologue with a longer chain (C12). The observation of this mechanism is related to smectic order fluctuations within N* phase whose amplitude is increased when approaching the SmC*–SmA–N* multicritical point.     

De Vries smectic A phase formed by a liquid crystal side chain copolymer? A 13C NMR study

We study the orientation and order parameter of a liquid crystalline random side chain copolymer by ¹³C NMR. Evidence has previously been presented that this material forms a de Vries smectic A phase. The NMR data show that the molecular tilt angle in the smectic A phase is very small or zero and the smectic A-smectic C* transition is attributed predominantly to a change of the molecular tilt rather than azimuthal ordering. We discuss the NMR results in the context of earlier X-ray and elastic characterizations of structurally similar materials.     

Coupling of liquid crystalline and polymer network properties in LC-elastomers

Electromechanical and electro-optical properties which result from an interplay of ferroelectricity and elasticity in slightly crosslinked ferroelectric liquid crystalline elastomers are studied in the vicinity of the smectic C-smectic A phase transition. In the chiral smectic C phase, the formation of the network during the crosslinking procedure stabilizes the polar orientation which is present. On heating the smectic C network into the chiral smectic A phase, an induced tilt is observed (mechanoclinic effect). The internal mechanical stress induced by the network formation appears to act like an external electric bias-voltage. The results are discussed in terms of a simple Landau model.     

Preliminary communication Helical superstructures in a novel smectic mesophase formed by achiral banana-shaped molecules

A new smectic type mesophase without in-plane order is presented which is formed by nitro substituted banana-shaped compounds. The structure of this phase is not yet known in detail. The growth of germs and also the textures point to a helicoidal structure. The helical structure is obviously the result of the chirality of the smectic layers which is caused by the tilt of the molecules together with the polar arrangement of the angled molecules.     

Stereochemical Rules Govern the Soft Self-Assembly of Achiral Compounds: Understanding the Heliconical Liquid-Crystalline Phases of Bent-Core Mesogens

A series of bent-shaped 4-cyanoresorcinol bisterephthalates is reported. Some of these achiral compounds spontaneously form a short-pitch heliconical lamellar liquid-crystalline phase with incommensurate 3-layer pitch and the helix axis parallel to the layer normal. It is observed at the paraelectric-(anti)ferroelectric transition, if it coincides with the transition from random to uniform tilt and with the transition from anticlinic to synclinic tilt correlation of the molecules in the layers of the developing tilted smectic phase. For compounds with long chains the heliconical phase is only field-induced, but once formed it is stable in a distinct temperature range, even after switching off the field. The presence of the helix changes the phase properties and the switching mechanism from the naturally preferred rotation around the molecular long axis, which reverses the chirality, to a precession on a cone, which retains the chirality. These observations are explained by diastereomeric relations between two coexisting modes of superstructural chirality. One is the layer chirality, resulting from the combination of tilt and polar order, and the other one is the helical twist evolving between the layers. At lower temperature the helical structure is replaced by a non-tilted and ferreoelectric switching lamellar phase, providing an alternative non-chiral way for the transition from anticlinic to synclinic tilt.     

On the origin of high optical director tilt in a partially fluorinated orthoconic antiferroelectric liquid crystal mixture

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A* (SmA*) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C* (SmC*) and smectic C_a* (SmC_a*) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA* phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC* phase, the distribution is biased such that the molecular tilt already present in SmA* now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmC_a* is about 20° larger than in SmA*. The large optical tilt (45°) in the SmC_a* phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations.     

Polar and quadrupolar order in smectic liquid crystals

In several smectic phases the long molecules are tilted towards the layer planes. The molecules in the layers of smectic C phases have a preferred tilt direction with a C2 rotation axis perpendicular to the tilt plane. If the molecules have a brick-like shape, a configuration possessing the D2h symmetry is also possible. For molecules shaped like chevrons or bananas, the existence of a smectic phase with the symmetry Cv was recently reported. We consider different in-plane configurations of smectics using a geometrical approach based on the 'scaled particle theory'. Varying the geometrical parameters of hard rod particles, a phase diagram for several smectic configurations is predicted. Depending on the particle shape, phases with dipolar order (C2,Cv) and quadrupolar order (D2h) can be stable.     

Thermal analysis of hydrogen bonded benzoic acid liquid crystals

Novel homologous series of supramolecular hydrogen bonded liquid crystals have been investigated. Hydrogen bonds are formed between p-n octyloxy benzoic acid and various p-n alkyloxy benzoic acids whose carbon chain length varied from pentyl to dodecyl. These complexes are characterized by Fourier transform infrared spectroscopy, polarizing optical microscopy (POM), and differential scanning calorimetry (DSC). Phase diagram is constructed from POM and DSC data. The order of the phase transitions is determined by Navard and Cox ratio (N _R). Characteristic phases like nematic, smectic C, and smectic F are identified. A new smectic ordering observed in this series is investigated by constructing phase diagram obtained from two binary mixtures of the present homologs. Inter-digitation of lamellar layers is observed to be one of the reasons for the occurrence of new smectic ordering. Optical tilt angle in smectic C phase is fitted to a power law. The magnitude of exponent of the power law is found to concur with the Mean Field theory predicted value.     

Systematic Variation of Length Ratio and the Formation of Smectic A and Smectic C Phases

The phase diagrams of four binary mixtures of chemically similar smectogenic mesogens differing only in molecular length are investigated. In these bidisperse systems the length ratio varies systematically. The phase diagrams show the stabilization of the smectic A and the destabilization of the smectic C phase with increasing length ratio as a general trend. Detailed small‐angle X‐ray diffraction and electro‐optic measurements revealed a decrease in smectic translational order and a continuous reduction of the tilt angle with increasing length difference. These surprising results are of general interest for the understanding of the structure and dynamics of smectic phases. The remarkably strong impact of the length difference on the smectic layer structure and the phase behavior is discussed from a mechanistic point of view taking into account sterical interactions. For the observed structural changes in these bidisperse smectics we propose pronounced out‐of‐layer fluctuations with increasing length difference as driving force, causing neighboring molecules within nearest layer into a smectic A‐like packing.     

Polar and quadrupolar order in smectic liquid crystals

In several smectic phases the long molecules are tilted towards the layer planes. The molecules in the layers of smectic C phases have a preferred tilt direction with a C2 rotation axis perpendicular to the tilt plane. If the molecules have a brick-like shape, a configuration possessing the D2h symmetry is also possible. For molecules shaped like chevrons or bananas, the existence of a smectic phase with the symmetry Cv was recently reported. We consider different in-plane configurations of smectics using a geometrical approach based on the 'scaled particle theory'. Varying the geometrical parameters of hard rod particles, a phase diagram for several smectic configurations is predicted. Depending on the particle shape, phases with dipolar order (C2,Cv) and quadrupolar order (D2h) can be stable.     

De Vries smectic A phase formed by a liquid crystal side chain copolymer? A 13C NMR study

We study the orientation and order parameter of a liquid crystalline random side chain copolymer by ¹³C NMR. Evidence has previously been presented that this material forms a de Vries smectic A phase. The NMR data show that the molecular tilt angle in the smectic A phase is very small or zero and the smectic A–smectic C* transition is attributed predominantly to a change of the molecular tilt rather than azimuthal ordering. We discuss the NMR results in the context of earlier X‐ray and elastic characterizations of structurally similar materials.     

Nano-segregated structures of hydrogen-bonded mesogens with perfluorinated moieties: cubic phase formation and first order smectic A to smectic C phase transition

Two series of mesogenic compounds having both a perfluorinated substituent and a hydrogen bonding active site were synthesized and their phase behavior investigated. Due to the chemical architecture of these materials exhibiting amphiphilic character, structures of nano-segregation are expected to form. We found a thermotropic cubic phase with Ia3d symmetry in one of the acid/base hydrogen-bonded complexes, which is a nano-segregated structure. Moreover materials exhibiting a first order smectic A to smectic C phase transition were found, which was ascertained by differential scanning calorimetry measuring a large latent heat, and X-ray diffraction experiments observing abrupt changes of physical properties at the phase transition, i.e. the tilt angle, the intensity and the half-width of the small angle reflection. This first order phase transition occurs due to the frustration of nano-segregated structures of lamellar phases.     

A racemic layer structure in a chiral bent-core ferroelectric liquid crystal

A fluid smectic phase of a chiral bent-core liquid crystal was found to have a ground state structure that is anticlinic in tilt and ferroelectric in polar order, SmC_AP_F*. The layer chirality of this structure alternates from layer to layer despite their being composed of chiral mesogens. Observations of the optical second harmonic generation signal from well-aligned domains confirm that the ground state of this phase is bistable ferroelectric. In addition to the ground state two types of metastable domains are also observed.     

Ferroelectric polysiloxane liquid crystals with 'de Vries'-type smectic A*-smectic C* transitions

We report preliminary results of optical and small angle X-ray scattering (SAXS) experiments on the smectic A*-smectic C* transition in two ferroelectric liquid crystalline polysiloxanes. Although the optical tilt angle in the SmC* phases reaches values up to 30°, temperature-dependent SAXS measurements clearly reveal that the smectic layer spacing is basically conserved during the A*-C* transition as well as in the subsequent C* phase. Connected with the A*-C* transition we further observed a significant increase in birefringence, hence reflecting an increase of orientational order. The practical absence of layer shrinkage and the enhanced orientational ordering are consistent with the de Vries diffuse cone model of smectic A-smectic C transitions.