IR spectra temperature changes and conformational structure of 4-butyl-4′-cyanobiphenyl

IR spectra of 4-butyl-4′-cyanobiphenyl in the liquid and solid-crystal states were measured in the 400–4000 cm^–1 region at 28–70°C. Changes of the spectra as a function of temperature are due to the conformational fluxionality of the molecules according to calculated IR spectra of the possible 4-butyl-4′-cyanobiphenyl conformers. Calculations were carried out using the method of fragments and the LEV-100 program package. Bands sensitive to the conformational changes in the molecular structure were found. IR spectra have been interpreted. Conclusions have been made about the conformations of the sample in the solid-crystal and liquid phases. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 325–333, May–June, 2009.     

Spectral properties of naphthalimide dyes mixed with 4-heptyl-4′-cyanobiphenyl (7CB) in Langmuir-Blodgett films

Langmuir-Blodgett (LB) films formed of some fluorescent dyes, namely derivatives of 4-aminonaphthalimide, and their binary mixtures with the liquid crystal 4-heptyl-4′-cyanobiphenyl (7CB) have been studied. The electronic absorption and fluorescence spectra were recorded. On the basis of these spectra, the spectral properties of the dyes and the intermolecular interactions in ultrathin ordered films were determined. The conclusions about the tendency to the creation of aggregates by dye molecules in LB films have been drawn. The measurements of absorption by using linearly polarised light have allowed us to determine the arrangement of the dye and liquid crystal molecules on the air-solid substrate interface.     

Pretransitional dielectric properties of nematogenic 4-cyanophenyl-4′-n-heptylbenzoate

This article presents results of the static and dynamic dielectric studies performed for mesogenic 4-cyanophenyl-4′-n-heptylbenzoate in the isotropic (I) and nematic (N) phases. Pretransitional phenomena are observed in the vicinity of I–N phase transition as an anomalous temperature behavior of both the static and the dynamic dielectric properties of the compound. The temperature dependence of the static permittivity is correlated with the entropy change induced by the probing electric field while an anomalous behavior of the dielectric relaxation directly points out for a subdiffusional Brownian rotation of mesogenic molecules in the vicinity of the phase transition.     

Studies on binary mixtures of 4-pentyloxy-4′-cyanobiphenyl with three 4, 4′-di(alkoxy)azoxybenzenes

Eighteen binary mixtures of 4-pentyloxy-4′-cyanobiphenyl (5OCB) and 4, 4′-di(alkoxy)azoxybenzenes (nOAB) with n = 5, 6, and 7 at different concentrations have been studied in detail. Over a wide concentration range, induced SmA phase was observed in all the mixtures except in one. In most of the mixtures, the refractive indices no, ne, and Δn lie between the values of pure components. The optical birefringence of the mixtures is found to decrease non-additively with concentration. The molecular polarizability anisotropy and the orientational order parameter <P₂> of the mixtures were calculated. Nature of variation of polarizability anisotropy with concentration is similar to that of Δn. In allmixtures <P₂> is more in smectic phase than in nematic phase and it also shows non-additive behaviour. Observed <P₂> values of the mixtures were compared with McMillan’s and Maier-Saupe theoretical values and good agreement is found in some mixtures. The transition temperatures obtained by fitting <P₂> data to McMillan’s theory agree with the observed values within a few degrees. Ratio of elastic constants K₃₃ and K₁₁ is determined for mixtures having nematic phase and found to diverge at T_NA transition point.     

X-ray studies of the smectic B phase of the 4-bromobenzylidene-4′-alkoxyanilines

The results of X-ray studies of the nine members (4?÷?12) of the 4-bromobenzylidene-4′-alkyloxyaniline homologous series (nBBAA) in smectic B (SmB) and smectic A (SmA) phases are presented. Interestingly, no SmC phase was identified. The thickness of smectic layers in the SmA and SmB phases was estimated showing unexpectedly that in SmA it is bigger than in the SmB. For the SmB phase, orthorhombic unit cell parameters were determined as a function of temperature. The obtained data are discussed in relation to rotational dynamics.     

Liquid-crystalline properties of 4-alkyl-, 4-alkyloxy and 4-halogene-4′-hydroxyazobenzene alkyloates

Twenty one esters, 4-alkyl-, 4-alkyloxy-, 4-nitro- and 4-halogene-4′-hydroxyazobenzne alkyloates have been synthesised. Basing on the DSC calorimetry and polarizing microscopy liquid- crystalline polymorphism was investigated. Five types of mesophases were identified: nematic, smectics A, C, F and unknown X (probably G).     

Physical properties of B_4N_4-Ⅰ and B_4N_4-Ⅱ:First-principles study

The structural, mechanical, electronic, mechanical anisotropy, and thermal properties of boron nitride(BN) polymorphs, such as B_4 N-4-Ⅰ and B4 N4-Ⅱ, are investigated under ambient pressure utilizing first-principles generalized gradient approximation calculations using an ultrasoft pseudopotential scheme. The phonon spectra and elastic constants reveal that B_4 N_4-Ⅰ is dynamically and mechanically stable at the pressure of 0 GPa and temperature of 0 K. Anisotropic calculations indicate that both B_4 N_4-Ⅰ and B4 N4-Ⅱ exhibit higher anisotropy of Young's modulus than cubic BN(c-BN). B_4 N_4-Ⅱ and B_4 N_4-Ⅰ present indirect and wide band gaps of 5.32 eV and 4.86 eV, respectively. In addition, B_4 N_4-Ⅰ is more brittle than B_4 N_4-Ⅱ. Moreover, the minimum thermal conductivity,κmin, of B4 N4-Ⅱ at 300 K is 1.92 W/(cm·K), which is slightly higher than those of B_4 N_4-Ⅰ and c-BN(1.84 W/(cm-K) and 1.83 W/(cm-K), respectively. However, κ_(min) of B_4 N_4-Ⅰ is slightly higher than that of c-BN.     

IR-Spectral Study of 4′-Substituted Phenylthiolbenzoates in Solution

A doublet structure of the C=O stretching band in the IR-spectra of 4′-methoxy-, 4′-methyl-and 4′-cyanophenylthiolbenzoate is proved. The solvatochromic effect on the intensities of both components suggests an equilibrium between two conformers with different dihedral angle determined by the plains of the benzene rings. The choice of the studied compounds is influenced by the fact that they are structural fragments of liquid crystals. The characterization of their rotameric preference in solution provides additional information about the influence of the terminal groups on the conformational mobility of the phenylthiolbenzoate skeleton as well as on the polarizability of the molecule.     

Dielectric properties of 4′-n-alkyl-4-cyanobiphenyls in their nematic phases

The principal dielectric constants of the pentyl to octyl derivatives of 4′-n-alkyl-4-cyanobiphenyl have been measured as functions of temperature in their nematic and isotropic phases. All the compounds exhibit a strong positive dielectric anisotropy due to the presence of a large dipole moment along the major molecular axis. The principal dielectric constantsε _‖ andε _⊥ as well as the anisotropy Δε decrease with increasing alkyl chain length. The experimental value of (ε_‖+2ε_⊥) decreases with decreasing temperature, and is throughout less than the extrapolated isotropic value, in conformity with the model of antiferroelectric short range order proposed by Madhusudana and Chandrasekhar.     

Oriental behaviour of some homologues of 4-n-pentyl-phenylthio-4′-n-alkoxybenzoate doped with dichroic dye

The long-range orientational order of three members of 4-n-pentylphenylthio-4′-n-alkoxybenzoate series doped with a dichroic dye was studied by means of electronic absorption and fluorescence measurements. The order parameters <P₂> and <P₄> as well as the orientational distribution function were determined on the basis of absorption and emission spectra of linearly polarized light recorded as a function of temperature in the nematic, smectic A, and smectic C phases. An influence of the dye molecular structure on the orientational order of the dye/liquid crystal mixture was observed. Moreover, the dependence of the order parameter values on the length of the alkoxy chain in liquid crystal molecules was found. It was shown that the order parameter <P₄>, obtained from fluorescence measurements, can be helpful in recognizing the second-order or weakly first-order transitions between various liquid crystalline phases.     

The Physical Tourist¶Historical Sites of Physical Science in Copenhagen

We provide a physical tour of Copenhagen focusing particularly on the sites associated with five great Danish scientists: Tycho Brahe (1546-1601), Niels Steensen (1638-1686), Ole Rømer (1644-1710), Hans Christian Ørsted (1777-1851), and Niels Bohr (1885-1962). We also point out the cemetery where prominent scientists are buried, and we note the location of the Carlsberg Honorary Residence.     

The phase behaviour of 4- n -pentylphenyl-4′- n -heptyloxythiobenzoate

New results of investigations of phase polymorphism for two substances, hydrogenous (7OS5-d₀) and partially deuterated (7OS5-d₂₆) have been presented. On the basis of measurements of the integrated “elastic window” intensity (EL), quasielastic neutron scattering (QNS) spectra and results obtained with the Transmitted Light Intensity (TLI) method, the metastable character of the SmC phase, that at constant temperature always transforms to the crystalline phase Cr₂, has been confirmed. Variations of the EL show a very clear hysteresis effect in the nematic and SmC phases as well as in solid phases. It was confirmed by a phase polymorphism in both investigated substances. Convergence of the EL and TLI methods was shown. The new phase situation of both hydrogenous and partly deuterated liquid crystals is presented.     

Smectic polymorphism of 4-decyloxybenzylidene- 4′-alkyloxyanilines and their mixtures with polar standards of mesophases

This article describes liquid crystalline properties of the homologous series of 4-decyloxybenzylidene-4′-alkyloxyanilines. Based on the polarization microscopy (POM and TOA methods) and the calorimetric (DSC) measurements a rich polymorphism has been detected. Investigated compounds exhibit nematic, smectic A, smectic C, smectic B, smectic I and G (smectic G) mesophases with their characteristic configurations. The presence of these mesophases was confirmed by the miscibility method, using 4-heptyloxybenxylidene-4′-pentylaniline as a mesophase reference. Nine other smectic standards with different polarity have been applied in order to investigate their influence on the mesophase stability.     

Theoretical estimation of mesogenic characteristics of 4-methyl (2′-hydroxy,4′-n-hexadecyloxy) azobenzene – a nematic liquid crystal

The compound 4-methyl (2′-hydroxy,4′-n-hexadecyloxy) azobenzene was synthesized by Prajapati and co-workers (Mol. Cryst. Liq. Cryst. 369 (2001), pp. 37–46). Subsequent experiments (D. Pal, [PhD thesis], University of Lucknow, Lucknow, India, 2007) confirmed that the compound exists in nematic phase for a small range of temperature (72°C–80°C). In the present work, optimization of molecular geometry has been carried out by employing the Gaussian 03 suit of programs without any constraint using density functional B3LYP along with 6-31G** basis set and checked for imaginary frequencies. A detailed investigation on intermolecular interaction energy at various interacting configurations has been carried out. In order to study the mesogenic characteristics of the molecule, an attempt has been made to estimate the variation of order parameter with respect to the change in temperature as well as degrees of freedom. These studies will be helpful to understanding the mesogenic character of any molecule prior to synthesis and promises future application in molecular engineering.     

Anisotropy Spectra of the Solvent-Sensitive Fluorophore 4-Dimethylamino-4′-Cyanostilbene in the Presence of Light Quenching

We examined the emission wavelength-dependent anisotropies of the solvent-sensitive fluorophore 4-dimethylamino-4-cyanostilbene (DCS) under conditions of light quenching by polarized time-delayed quenching pulses. Illumination on the long-wavelength side of the emission spectrum with time-delayed light pulses resulted in a progressive decrease in the emission anisotropy as the observation wavelength increased toward the stimulating wavelength. The anisotropy changes of DCS were most wavelength dependent when spectral relaxation occurred during the excited-state lifetime. Light quenching of DCS in a low-viscosity solvent revealed no wavelength-dependent anisotropies. Control measurements using a solvent-insensitive fluorophore did not show any wavelength-dependent anisotropy with light quenching. The data for DCS can be explained by a model which allows wavelength-selective quenching of the long-wavelength emission formed by time-dependent spectral relaxation. These results indicate that polarized light quenching can be used to study systems which display multiple emissions and/or time-dependent spectral shifts.     

Phase behavior of four homologous compounds of 4-n-alkyl-4′-isothiocyanatobiphenyl (nBT) under pressure

The phase behavior of four homologous compounds of 4-n-nonyl-, 4-n-decyl-, 4-n-undecyl-, and 4-n-dodecyl-4′-isothiocyanatobiphenyl (9BT, 10BT, 11BT, and 12BT) was reinvestigated to characterize their high-pressure mesophases under pressures up to 150 MPa using a polarizing optical microscope equipped with a high-pressure optical cell and a wide-angle X-ray diffractometer equipped with a high-pressure sample vessel. The pressure-induced mesophases of 9BT and 10BT appearing under pressures above about 60 and 100 MPa, respectively, were identified as nematic (N) and smectic A (SmA) phases, which indicate the reversible Cr–CrE–N–I and Cr–CrE–SmA–I phase transitions under elevated pressure. Both the 11BT and 12BT exhibited the reversible transition of Cr–CrE–SmA–I in the low-pressure regions below about 5 and 23 MPa, respectively. Both the stable CrE phases changed into the monotropic (and metastable) one under higher pressures, which the Cr–SmA–I and I–SmA–CrE–Cr phase transitions on heating and cooling processes were recognized, respectively.     

Phase behavior of four homologous compounds of 4-n-alkyl-4′-isothiocyanatobiphenyl (nBT) under pressure

The phase behavior of four homologous compounds of 4-n-nonyl-, 4-n-decyl-, 4-n-undecyl-, and 4-n-dodecyl-4′-isothiocyanatobiphenyl (9BT, 10BT, 11BT, and 12BT) was re-investigated to characterize their high-pressure mesophases under pressures up to 150 MPa using a polarizing optical microscope equipped with a high-pressure optical cell and a wide-angle X-ray diffractometer equipped with a high-pressure sample vessel. The pressure-induced mesophases of 9BT and 10BT appearing under pressures above about 60 and 100 MPa, respectively, were identified as nematic (N) and SmA phases, which indicate the reversible Cr–CrE–N–I and Cr–CrE–SmA–I phase transitions under elevated pressure. 11BT and 12BT exhibited the reversible transition of Cr–CrE–SmA–I in the low-pressure regions below about 5 and 23 MPa, respectively. Both the stable CrE phases changed into the monotropic (and metastable) one under higher pressures, in which the Cr–SmA–I and I–SmA–CrE–Cr phase transitions on heating and cooling processes, respectively, were recognized.