Anomalous phase sequence in new chiral liquid crystalline materials

We have prepared and studied a series of rod-like liquid crystalline compounds with the molecular core laterally substituted by bromine atom and with the lactate unit in the chiral terminal chain. Microscopic observation under the polarising microscope, x-ray and dielectric spectroscopy results enable us to establish the TGBA–SmA–TGBA_RE–TGBC phase sequence. The presence of the re-entrant TGBA phase below the regular SmA phase, found for three homologues, is quite uncommon. Results are discussed and compared with the previously studied compounds with regular phase sequences.     

Synthesis and mesomorphic properties of new compounds exhibiting TGBA and TGBC liquid crystalline phases

We synthesised a series of rod-like mesogens with a (S)-2-methylbutyl-(S)-lactate unit in the chiral chain that exhibited extremely wide temperature ranges in the TGBA and TGBC* phases. TGB phases were identified, based on typical textures in confined samples and in free-standing films, by Grandjean-Cano texture and by NMR studies on a deuterium-labelled isotopomer. A sufficiently high electric or magnetic field transformed the TGBA and TGBC* phases into their respective SmA and SmC* phases, the TGB structures being restored within some 20-30 minutes. Therefore values of the spontaneous polarisation and spontaneous tilt angle, when measured under a sufficiently high field, gave evidence of the properties of the SmC* phase. Temperature dependencies of relaxation frequency, dielectric strength, selective reflection and layer spacing showed anomalies at a certain temperature within the TGBC* phase range. Also, changes in textures, as well as in ²H-NMR spectra, occurred at this same temperature. These results suggest the existence of two TGBC* phases.     

Synthesis and mesomorphic properties of chiral fluorinated liquid crystals

Some fluorinated chiral liquid crystals were synthesized and the compounds characterized by IR, ¹H NMR, ¹⁹F NMR and mass spectroscopy and elemental analysis. Their phase transition behaviour was investigated by differential scanning calorimetry and polarizing optical microscopy. Nearly all of the compounds synthesized are liquid crystals with an enantiotropic cholesteric phase. Some of them exhibit a blue phase. Lateral tetrafluoro substitution decreases the clearing point and molecular polarity affects the formation of liquid crystalline phases.     

Dynamics in ferro- and antiferroelectric phases of a liquid crystal with fluorinated molecules as studied by dielectric spectroscopy

For 1-[3-fluoro-4-(1-methylheptyloxycarbonyl)phenyl]-2-[4-2,2,3,3,4,4,4-heptafluorobutoxybutoxy)biphenyl-4-yl]ethane (1F7), built of chiral molecules, results of dielectric measurements of liquid-crystalline and solid phases are presented. Rich polymorphism of liquid-crystalline (SmC*, SmC*_A and SmI*_A) phases as well as of solid (Cr1 and Cr2) phases were observed down to –130°C. At a frequency range from 0.1 Hz to 3 MHz, the relaxation processes were detected in ferroelectric SmC*, antiferroelectric SmC*_A and highly ordered SmI*_A smectic phases. The mechanism of complex dynamics (moleculear and collective) was identified with the help of the bias field. Vitrification of conformationally disordered crystal phase Cr2 was found in accordance with calorimetric observations.     

3D mapping of the output laser beam from a PDLC sample

Self-transparency due to thermal non-linearities is presented as a basic switching effect in a thick polymer dispersed liquid crystal sample. For the first time a detailed 3D mapping of the output laser beam as a function of the x-y coordinates is presented: changes of the transmitted beam profile are recorded vs. both incident power and time. It is discussed how light intensity and temperature can be used as control parameters for the non-linear part of the refractive index. The experimental results confirm the existence of a threshold value of the incident light intensity at which the device switches from the scattering state to the transmissive state.     

Electroclinic effect around a smectic A-chiral nematic phase transition

We present measurements of the dynamics of the electroclinic effect around a smectic Achiral nematic transition. The phenomenon has been studied between 1 kHz and 1 MHz, extending by one order of magnitude the frequency range of previous studies. The results have unambiguously allowed us to distinguish two additive mechanisms in the generation of the optical tilt. A model to explain the physical origin of both mechanisms is presented. The first mechanism (fast) is the only bulk process intrinsic to the material and behaves normally at the transition, in the sense that both the magnitude of the tilt as well as the relaxation time have the expected temperature dependence. On the other hand, the second mechanism (slow) is not properly an electroclinic effect, but a surface-mediated effect driven by elastic forces. This explains the apparent anomalous behaviour of the phenomenon reported in the literature one decade ago.     

Towards a new class of ferroelectric liquid crystal molecules for nonlinear optical applications

The synthesis of a new molecule specifically designed to exhibit both ferroelectric and nonlinear optical properties is presented. This molecule possesses an optically active phenyl sulphinic group, which introduces a dipole moment directly linked to the chromophore group, with a nitro group in the meta -position. The rest of the molecule comprises a tolane and a benzoate group. Such a structure results in an enantiotropic smectic C*-smectic A phase sequence in its polymorphism. A first measurement of the spontaneous polarization shows a high value. The polymorphism of the racemic homologous molecule possessing the nitro group in the ortho-position is also presented, and also shows the smectic C-smectic A phase sequence.     

Morphological studies of a (self-assembling oil gelator/liquid crystal) composite system

The aggregation structure of a novel (self-assembling oil gelator/liquid crystal) composite was investigated using light scattering studies and morphological observations. The oil gelator forms a self-assembled-networks aggregate in an organic solvent with a low molecular weight liquid crystal (LC). It became apparent from Hv light scattering patterns and polarizing optical microscopy that two types of LC molecular alignments exist in the composite: a random orientation and a spherulite type one in a nematic gel state. Also, optical and atomic force microscopic observations revealed that fibrils which formed bundles in the fibre-like and spherulite-like aggregates, were formed in the composite. The alignment of the liquid crystal molecules was related to the aggregation structure of the self-assembling oil gelator in a liquid crystal gel state.     

Dielectric properties near the isotropic-smectic-C* phase transition

The dielectric properties in the vicinity of the isotropic-smectic-C* phase transition in ferroelectric liquid crystals are discussed. The temperature and frequency dependence of the complex dielectric permittivity in both the phases of the transition are calculated. The theoretical phase diagram of the dielectric permittivity is studied.     

The effect of the alkyl chain length on the mesomorphic properties of new lactic acid derivatives

New series of lactic acid derivatives with alkyl terminal chain have been synthesised and their mesomorphic properties studied. We have varied the length of chiral and non-chiral terminal alkyl chains and found that prolonging both chains has a strong effect on the SmA*–SmC* phase transition. Most of the new materials exhibit only paraelectric SmA* phase; for homologues with a longer non-chiral chain (m ≥ 10), the ferroelectric (SmC*) phase appears below the SmA* on cooling and persists down to a room temperature. The role of the chiral terminal chain in the molecule is quite opposite – only its short length supports the existence of ferroelectric phase. Additionally, a hexatic phase appeared below the SmA*–SmC* phase sequence for several homologues at low temperatures. All materials have been studied using standard experimental techniques (differential scanning calorimetry (DSC), texture observations, polarisation and tilt angle measurements, etc.). Liquid crystalline properties of new materials have been compared with the previously prepared and studied lactic acid derivatives.     

Multiple Polar and Non-polar Nematic Phases

Liquid-crystal materials exhibiting up to three nematic phases are reported. Dielectric response measurements show that while the lower temperature nematic phase has ferroelectric order and the highest temperature nematic phase is apolar, the intermediate phase has local antiferroelectric order. The modification of the molecular structure by increasing the number of lateral fluorine substituents leads to one of the materials showing a direct isotropic-ferronematic phase transition.     

A simple electro-optic technique for studying the electroclinic effect in the smectic A* phase

The critical behaviour of the electroclinic response in the chiral smectic A* phase in the vicinity of the second-order smectic A* to smectic C* phase-transition temperature has been investigated using a new electro-optic technique. The temperature variation of the electroclinic coefficient, the relaxation frequency and the coefficient of the quartic term in the tilt angle in the Landau free energy expansion have been studied. The electroclinic coefficient diverges with decreasing temperature as the smectic A* to smectic C* phase-transition temperature is approached with a critical exponent, as predicted in the mean field Landau theory. The measured quartic coefficient varies strongly with temperature, contrary to the usual assumptions of the mean field Landau theory.     

Dielectric spectroscopy of polyazomethine with vinylene moieties in the main chain

We have explored the dielectric properties of polyazomethine with vinylene moieties in the main chain (PAZ-PV). The dialdehyde 2,5-bis(hexyloxy)-1,4-bis[(2,5-bis(hexyloxy)-4-formyl-phenylenevinylene]benzene was polymerised in solid-state with the diamine poly(1,4-butanediol)bis(4-aminobenzoate). The polymer obtained exhibited liquid crystal properties. The molecular dynamics and phase transitions including the liquid crystal phase of PAZ-PV were investigated by dielectric spectroscopy. The dielectric constant decreases with a decrease in the temperature, except in the nematic phase region, where a slight increase was observed. The temperatures of the phase transitions were well seen and were compared with differential scanning calorimetry (DSC) and polarised optical microscopy experiments. All values determined from dielectric data were a few degrees higher than those obtained in previous measurements (DSC).     

New aromatic azo compounds: syntheses and liquid-crystalline properties

The chemical syntheses of 12 new azo dyes are reported. The optically active compounds were prepared by the Mitsunobu reaction, amide formation, and esterification with optically active alcohols or acids. Several new compounds showed liquid-crystalline properties, and their phase transition behavior was investigated.     

The structure of acrolein in a liquid crystal phase

The (1)H NMR spectrum of a sample of acrolein dissolved in the nematic liquid crystal phase I52 has been analysed to yield 18 dipolar couplings between all the magnetic nuclei in the molecule; moreover, the (13)C and (13)C{(1)H} NMR spectra of a sample of acrolein in CDCl(3) were recorded and analysed to determine the indirect J(ij) couplings. The data were used to obtain the relative positions of the carbon and hydrogen atoms, assuming that these are independent of the conformations generated by rotation around the C--C bond through an angle phi, and to obtain a probability distribution P(phi). It has been found that in the liquid phase, the distribution is a maximum at the trans form whereas the abundance of the cis form is significantly smaller compared with that found by microwave spectroscopy or high level quantum mechanical calculations. Such calculations produced also a suitable force field needed to develop suitable strategies for vibrational correction procedure in the case of flexible molecules.     

Polymerizable hexacatenar liquid crystals containing a luminescent oligo(p-phenylenevinylene) core

Polymerizable hexacatenar mesogens containing a photo-active oligo(p-phenylenevinylene) core were successfully synthesized by replacing the traditional n-alkoxy tails on the molecules with polymerizable hydrocarbon tails containing terminal isoprenyl or 1,3-dienyl units. It was found that for this particular liquid crystal (LC) platform, the incorporation of conventional radical polymerizable groups such as acrylates in the tails was not conducive to the formation of thermotropic LC phases, presumably due to their polar nature. The resulting photoluminescent isoprenyl and 1,3-dienyl hexacatenar monomers were found to form columnar hexagonal phases at elevated temperatures (c. 45–75°C), as determined by powder X-ray diffraction. Unfortunately, photoinitiated radical polymerization studies revealed that the mesogens are susceptible to photodegradation in the LC state at elevated temperatures, resulting in the loss of both LC order and emission properties during photopolymerization. Thermally initiated radical polymerization in the absence of light, however, afforded effective crosslinking with retention of both LC order and the desired emission properties. The resulting crosslinked columnar hexagonal phases were found to exhibit emission maxima at nearly identical wavelengths, with comparable intensities relative to the unpolymerized starting materials. The effect of the different polymerizable groups on the mesogenic behaviour, polymerization characteristics, and emission properties of the hexacatenar compounds is presented.     

Effect of lactate group in the chiral chain of new compounds exhibiting short-pitch cholesteric or TGBA phase

We have synthesised and studied lactic acid derivatives based on chlorine substituted molecular core, which is created from two biphenyls linked by an ester, and terminated with one or two lactic units in a chiral chain. The compounds with one lactate group exhibit cholesteric phase with rather short helix pitch (200 nm) in a broad temperature range. On contrary, compound with two lactate units reveals a stable TGBA phase, with transition temperatures substantially lower than those for one-lactate derivatives. We have studied mesophase behaviour and electro-optical properties, mostly based on the texture observation in polarising microscope. Additionally, we have used AFM and x-ray techniques to confirm mesophase identification and establish structural properties.     

Thermal behavior of selected ferroelectric liquid crystals

Thermal properties of three ferroelectric liquid crystals, namely: 3-octyloxy-6-[2-fluor-4-(fluoroctyloxy)phenyl]-pyridine (FFP), 3-(3-fluor-nonyl)-6[4-heptyloxyphenyl]-pyridine (FNHPh-P), 4-[(S,S)-2,3-epoxyhexyloxy]phenyl 4-(decyloxy)benzoate (EHPhDB) were studied using heat flux differential scanning calorimetry method. All the transitions expected in this compounds, except the SmC^*-SmA^* and SmC^*-S₃ transitions, were detected in the DSC curves. The temperatures of the phase transitions and the enthalpy changes associated with them were determined. The transition from the liquid crystalline to the crystalline state showed significant hysteresis for all three compounds studied. The following transitions: SmA^*-Is, SmG^*-SmC^* for FNHPh-P, N^*-Is for EHPhDB, N^*-Is and SmC^*-N^* for FFP also showed a small hysteresis basing on which first-order character of all the above transitions was implied. All three substances studied in this work are characterized by a complex polymorphism in the solid state.The author is grateful to Dr. Stanislaw Wróbel for his stimulating interest, valuable discussions and supplying the samples. This work has been done in the framework of the KBN grant 2 P302 139 07.     

Kinetically controlled phase transitions in liquid‐crystalline polymers. II. Isothermal degradation of ferroelectric switching in a chiral side‐chain polysiloxane during slow smectic B phase formation

The kinetics of phase transformations in a chiral siloxane polymer has been studied with an Avrami analysis of the differential scanning calorimetry data. Ferroelectric switching has been measured as a function of the driving voltage and temperature. The evolution of the switching at a constant temperature has been studied within the temperature range of the kinetically governed smectic C*/smectic B phase transition. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1779–1784, 2005