EPR anisotropy induced by a magnetic field in the smectic A phase of a mesogenic Cu(II) complex derived from a Schiff's base

The Q-band electron paramagnetic resonance (EPR) spectrum of the frozen smectic phase of the mesogenic compound bis[N -(4'-n-pentoxyphenyl)-4-n-decyloxysalicylaldiminate] copper(II) is studied. An anisotropic EPR spectrum is observed if freezing from the SmA phase is done in the presence of a magnetic field; the sample tends to orient with the director perpendicular to the magnetic field. The relative intensities of the EPR signal of this exchange coupled system are discussed in relation to the orientational distribution of the molecules. The results appear to be compatible with a biaxial magnetic susceptibility in the SmA phase. This suggests that an ordering of the short axes of the molecules in the plane perpendicular to the director in the SmA mesophase may take place.     

The structure and conformation of a mesogenic compound between almost zero and almost complete orientational order

The conformational distributions in molecules that form liquid crystalline phases are predicted to depend strongly on orientational order. Results are presented here to test this hypothesis. The mesogen 4-hexyloxy-4'-cyanobiphenyl (6OCB) has been studied by NMR spectroscopy in the isotropic phase and in the nematic phase. In the isotropic phase the field-induced orientational ordering produces small dipolar couplings between ¹³C and ¹H nuclei, which were determined from the ¹³C spectra. Couplings between ¹H nuclei were also obtained using 2D selective refocusing experiments. In the nematic phase, both ¹H-¹H dipolar couplings and quadrupolar splittings for deuterium nuclei were measured for partially-deuterated samples. Both proton and deuterium spectra were also obtained for 6OCB in an equimolar mixture with 4-(ethoxybenzylidene)-4'-butylaniline (EBBA). This mixture exhibits SmA and SmB phases. The data obtained from these experiments has been analysed to yield the probability distribution of the conformations in this molecule generated by rotations about bonds. It is found that there is a substantial influence of the orientational order of the molecules on these distributions.     

NMR determination of smectic ordering of probe molecules

The NMR spectra of the three solutes ortho-, meta-, and para-dichlorobenzene in the nematic and smectic A phases of the liquid crystals 8CB and 8OCB are analyzed to yield two orientational order parameters for each solute. Extrapolation of the asymmetry in the energy parameters that describe the orientational ordering in the nematic phase are used to provide estimates of the strength of the nematic potential in the smectic A phase. The experimentally determined asymmetry of the orientational order parameters in the smectic A phase is then used in conjunction with Kobayashi-McMillan theory applied to solutes to give information about the smectic A layering and the nematic/smectic A coupling. In both smectic A solvents, the solute smectic coupling constant, tau, is negative (with the origin fixed at the center of the smectic layer) for all solutes. The signs and relative values of tau indicate that the ortho and para solutes favor the interlayer region while the meta solute is more evenly distributed throughout the layers.     

2H NMR spectroscopy of liquid crystals: structure and orientational order of a chiral smectogen in its A, C* and J* phases

²H NMR spectroscopy is employed to investigate the orientational order, molecular structure and phase transitions of the chiral smectic liquid crystal 1-methylheptyl 4'-(4-n-decyloxybenzoyloxy)biphenyl-4-carboxylate (10B1M7), showing smectic A, C* and J phases, as well as several sub-smectic C* phases. Two optically pure, differently deuteriated isotopomers have been purposely synthesized and studied.     

Flexible taper-shaped liquid crystal trimer exhibiting a modulated smectic phase

We prepared some taper-shaped liquid-crystalline trimers in which two phenylpyrimidine units and a 1,4-diphenyl-2,3-difluorobenzene unit are connected to 2,4-dihdroxy benzoic acid via flexible spacers. We then investigated their liquid-crystalline properties using polarised optical microscopy, differential scanning microscopy and X-ray diffraction. 6-[4–(5-Octylpyrimidin-2-yl)phenyloxy]hexyl 2-{7-{4-[4–(4-hexylphenyl)-2,3-difluorophenyl]phenyloxy}heptanoyloxy}-4-{6-[4–(5-octylpyrimidin-2-yl)phenyloxy]hexyloxy}benzoate (1) was found to exhibit a phase sequence of isotropic liquid – nematic – intercalated smectic A – intercalated anticlinic smectic C – modulated smectic C. The structure–property relation in the taper-shaped trimers reveals that the modulated phase is induced by competition between an intercalated structure stabilised by dipole–dipole interaction and a monolayer structure by packing entropy effects. Conformational change of compound 1 induced by intermolecular interactions plays an important role in the phase transition behaviour.     

Optical microscopy, DSC and X-ray diffraction studies in binary mixtures of 4-pentyloxy-4'-cyanobiphenyl with three 4,4'-di(alkoxy)azoxybenzenes

A large number of binary mixtures of 4-pentyloxy-4'-cyanobiphenyl (5OCB) and 4,4'-di(alkoxy)azoxybenzenes (nOAB) with n = 5, 6 and 7 have been studied by optical microscopy, DSC and X-ray diffraction methods. Over a wide concentration range the smectic A (SmA) phase is induced and the nematic (N) phase of the parent compounds is absent. Instead of the tilted smectic C phase of 7OAB an orthogonal SmA phase is observed when only 12% of the host molecules are replaced by 5OCB molecules. Moreover, in some mixtures the thermal stability of the induced SmA phase is found to be more than 1.6 times the stability of the mesophses in the pure compounds. The N-isotropic or Sm-I transition temperatures slowly increases with increasing concentrations, reaching a maximum at x _5OCB = 0.50 and then falling quite rapidly. In all the mixtures the enthalpy changes at the N-I transitions follow the simple additivity rule. In no mixture, except mixture C2, could the SmA-N transition be detected by DSC, although in all the mixtures the ratio T _NA/T _NI is found to be more than 0.95, which is in contradiction to McMillan's theory. Average intermolecular distances are found to have a minimum value near the equimolar concentration. From the concentration dependence of the smectic layer spacings it also appears that in all the mixtures the smectic A_d phase evolves from the smectic A₁ phase with increasing concentrations.     

Hole mobility and lifetime in a smectic liquid crystalline photoconductor of a 2-phenylnaphthalene derivative

We have investigated hole transport properties in the smectic mesophases of a 2-phenylnaphthalene derivative 6-(4'-octylphenyl)-2-dodecyloxynaphthalene in detail by using time-of-flight technique. The transient photocurrents were measured in liquid-crystal cells with various thickness from 5 to 700 microm. They were well defined and nondispersive in the smectic A (SmA) phase up to 500 microm and in the smectic B (SmB) phase within the entire thickness employed, while they exhibited an exponential decay in the SmA phase at 700 microm. The mobilities in the SmA and SmB phases were constant in each mesophase irrespective of the cell thickness, and were 2.5 x 10(-4) and 1.7 x 10(-3) cm2V s, respectively. The hole lifetimes were determined to be 10 ms and longer than 5 ms for the SmA and SmB phases, respectively. We discuss the origin of these lifetimes from the two points of view, i.e., hole trapping by a trace amount of existing impurities and recombination with negative ionic charges. We conclude that impurities are mainly responsible for the present hole lifetime test.     

Sixfold bond orientational properties of a model liquid crystal in the dimensional crossover of B phases: a computer simulation study

A wide range of NPT simulations of a bead necklace liquid crystal model in the crystal B, smectic B, smectic A, and nematic phases have been performed. Systems with up to 21 600 molecules have been studied to observe the behavior of slowly decaying spatial correlation functions. The pair correlation function and its in-plane restriction are consistent with a crystalline phase made of independent two-dimensional crystalline layers. Smectic B phase is studied by the bond orientational pair correlation functions g(6) and its extension g(6ext). The first reaches a constant value, which seems to rule out a classical hexatic phase. The latter shows a power-law decay within the layers: its typical decay exponent (eta(6ext)) is evaluated. Relationships between multiple harmonics of the C(6n) order parameter have been evaluated through the whole range of existence of B phases (crystalline and smectic): the extension to the crystalline phase holds and provides an excellent fit of the simulation data.     

Effect of terminal polar substituents on the nature of smectic A liquid crystals of a series of 4-(4'-octyloxybenzoyloxy)benzylidene-4'-substituted anilines

The nature of smectic A liquid crystals and the phase transitions from smectic A to nematic phases are studied in the homologous series of 4-(4'-octyloxy-benzoyloxy)benzylidene-4'-substituted anilines, in which the substituents are H, F, Cl, Br, I, NO₂ and CN. Measurements have been performed for the dipole moment of the molecule, the smectic A lattice period, the temperatures and the entropies of phase transitions, and the temperature dependence of the orientational order parameter, all of which provide information on the intermolecular pair potentials. It is shown that the introduction of a terminal polar substituent brings about counteracting contributions to the stability of the smectic A state. It is suggested that the reentrant nematic phase transition can appear in the strongly polar mesogens if the extent of antiparallel association of the molecules increases on lowering the temperature.     

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.     

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.     

Reinvestigation of carrier transport properties in liquid crystalline 2-phenylbenzothiazole derivatives

We have reinvestigated the charge carrier transport properties in a liquid crystal of 2-(4'-heptyloxyphenyl)-6-dodecylthiobenzothiazole (7O-PBT-S12), for which the electronic conduction was first established in rodlike liquid crystals and for which the highest hole mobility in the smectic A (SmA) phase ever achieved was reported. We found that 7O-PBT-S12 exhibited three crystal phases, one of which appeared in a limited temperature range of 10 degrees just below the phase transition temperature from the SmA phase. In this crystal phase, nondispersive transient photohole currents were observed in time-of-flight experiments, and its hole mobility was determined to be 8 x 10(-3) cm(2)/Vs, slightly higher than that reported previously in the SmA phase. For the SmA phase, however, the hole mobility was 1 x 10(-4) cm(2)/Vs. Furthermore, we established the electron transport in the SmA phase of purified 7O-PBT-S12, whose mobility was the same as the hole mobility in that phase. In order to confirm generality of the new findings in 7O-PBT-S12, we investigated the carrier transport properties of its derivative having a short hydrocarbon chain, 2-(4'-heptyloxyphenyl)-6-butylthiobenzothiazole (7O-PBT-S4), and obtained comparable results. The present results correct a mistake in the previous report and give an idea of what a typical mobility in the SmA phase is. On the basis of these results, we discuss what determines the charge carrier mobility in smectic mesophases.     

2H NMR spectroscopy of liquid crystals: structure and orientational order of a chiral smectogen in its A,C* and J* phases

²H NMR spectroscopy is employed to investigate the orientational order, molecular structure and phase transitions of the chiral smectic liquid crystal 1-methylheptyl 4'-(4-n-decyloxybenzoyloxy)biphenyl-4-carboxylate (10B1M7), showing smectic A, C* and J phases, as well as several sub-smectic C* phases. Two optically pure, differently deuteriated isotopomers have been purposely synthesized and studied.     

Solute-Solvent Interactions in the Nematic and Smectic A Phases of 4 4-di-n-Heptylazoxybenzene Studied by Deuteron NMR

The orientational order parameters have been measured by deuteron N.M.R. of both solute (at low dilution) and solvent in various binary mixtures involving the liquid crystal 4,4'-di-n-heptylazoxybenzene (HAB). The solutes studied were azoxybenzene-d₁₀ and n-heptylbenzene-d₇ which are fragments of HAB, azobenzene-d₁₀ because of its similarity to azoxybenzene, and anthracene-d₁₀ because of its known structure and symmetric shape. The major and biaxial order parameters of the solutes are analysed in terms of a molecular field model for the potential of mean torque for biaxial particles. The behaviour of the solute order parameters on approaching and entering the smectic A phase is interpreted in terms of a temperature and phase dependent partitioning of the solute between aromatic and aliphatic regions of the solvent.     

Synthesis and properties of three novel series of monomers containing para-methoxyazobenzene as the mesogenic group

Three novel series of monomers, namely n-1-bromo-[4-(4-methoxyphenylazo)phenyloxy]-alkanes (Bn, n = 3, 6, 10), n-[4-(4-methoxyphenylazo)phenyloxy]alkyloxy-4-methoxybenzene (Cn, n = 3, 6, 10) and n-[4-(4-methoxyphenylazo)phenyloxy]alkyloxy-[4-methoxy-2,5-bis(chloromethyl)]benzene (Dn, n = 3, 6, 10) were synthesized and characterized with FTIR, ¹H NMR, UV-visible and fluorescence spectroscopy. Their thermal behaviour was studied by different scanning calorimetry and polarizing optical microscopy. The results show that B3, B6 and C6 exhibit monotropic nematic liquid crystalline behaviour.     

New liquid crystalline phases with layerlike organization

Novel lamellar mesophases which are quite distinct from conventional smectic mesophases were obtained with a bolaamphiphilic triblock molecule composed of a rigid biphenyl core, two polar 2,3-dihydroxypropoxy groups in the terminal 4- and 4'-positions, and a semiperfluorinated chain [O(CH2)6C10F21] in the lateral 3-position. The competitive combination of microsegregation and rigidity in this molecule leads to layer structures in which the bolaamphiphilic cores segregate from the lateral chains into distinct sublayers. In these sublayers the biphenyl cores are aligned parallel to the layer planes. Decreasing the temperature leads to a subsequent inset of orientational and positional order of the biphenyl unit, which leads to a transition from an uniaxial SmA phase to a biaxial SmAb phase and finally to a mesophase with an additional periodicity within the aromatic sublayers. Here, microsegregation occurs on two distinct levels: The segregation of the nonpolar chains from the aromatic cores leads to the "bulk" layer structure and segregation of polar and aromatic subunits within the aromatic sublayers gives rise to an additional periodicity within the aromatic sublayers. These phases can be regarded as smectic phases built up by quasi-2D layers with nematic, respectively SmA-like order, separated by isotropic layers of the lateral chains.     

X-ray diffraction study on liquid crystals from 4-hexylphenyl 4-cyanobenzoyloxybenzoate and 4-heptyloxyphenyl 4-cyanobenzoyloxybenzoate

X-ray investigations were performed on 4-hexylphenyl 4-cyanobenzoyloxybenzoate (DB6CN) and on 4-heptyloxyphenyl 4-cyanobenzoyloxybenzoate (DB7OCN). For both compounds, the smectic A₂ structure is observed. From the small angle meridional reflections, the angular distribution of the smectic units around the normal to the smectic layers and the longitudinal correlation length were studied. The orientational order parameter is calculated from the wide angle equatorial reflections. Based on the assumption of a layer structure with undulation in the liquid crystalline smectic A phase, the relationship between the dimensionless parameters χch/dL (correlation length/thickness of the smectic layer) and FWHM/2θ₀ (full width at the half maximum/maximum point of the scattering peak) is simulated.     

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.     

Non-symmetric chiral isoflavone dimers: synthesis,characterisation and mesomorphic behaviour

A new series of non-symmetric chiral isoflavone-based liquid crystalline dimers, α-(2-methylbutyl-4′-(4″-phenyloxy)benzoate)-ω-(3-(4′-decyloxyphenyl)-4H-1-benzopyran-4-one-7-oxy)alkanes, with 3–12 carbon atoms in the alkyloxy spacer, have been synthesised. A pronounced odd–even effect for the phase transition temperatures upon varying the spacer length was observed. The short dimers exhibited monolayer smectic A (SmA) and smectic C (SmC*) phases while for longer homologues a chiral nematic (N*) phase was found. The temperature range of the nematic phase was broadened with elongation of the alkyl spacer. Stabilisation of the nematic phase resulted from competition between the monolayer and intercalated smectic structures. The SmA–SmC* phase transition was second order for all studied compounds with a cross over to the de Vries type behaviour for the shortest homologue.     

Structural ordering and spectral properties of smectic A with biaxial solute molecules

The influence of (i) orientational-translational ordering of solvent and solute molecules, (ii) anisotropic intermolecular solute-solvent interactions and (iii) the features of the electronic structure of biaxial solute molecules dissolved in a smectic A phase on the spectral position of polarized bands of a solute electronic absorption has been investigated. Equations for the positional-orientational pseudopotential in a pure smectic A doped with biaxial solute molecules have been obtained within the framework of the molecular statistical approach. The question about the correlation of contributions of partial orientational and translational molecular ordering to the spectral properties of a molecular system has been answered.