Odd-Even Effects in the Dielectric Properties of Nematics 4-(Trans-4′-N-Alkylcyclohexyl)Isothiocyanatobenzenes

Abstract

The anisotropy of the static electric permittivity and conductivity for the homologous series of nematics: 4-(trans-4′-n-alkylcyclohexyl)isothiocyanato-benzenes (n-CHBT) for n = 3–10 have been measured. It is shown that the odd-even effect in the dielectric anisotropy Ac is related to the perpendicular component of electric permittivity. The odd-even effect is found in n-CHBT for both the anisotropy in the conductivity and the activation energy for ionic movement.     

Dielectric and switching properties of a highly tilted AFLC material (S)-(+)-4-(1-methylheptyloxycarbonyl)-2,3-difluorophenyl 4′-[3-(2,2,3,3,4,4,4-heptafluorobutoxy)prop-1-oxy]biphenyl-4-carboxylate

Thermodynamic, dielectric, optical and switching parameters of a single-phase antiferroelectric (AF) liquid crystalline material (S)-(+)-4-(1-methylheptyloxycarbonyl)-2,3-difluorophenyl 4′-[3-(2,2,3,3,4,4,4-heptafluorobutoxy)prop-1-oxy]biphenyl-4-carboxylate have been studied. These studies show wide temperature range (~97.8°C–25.3°C) of AF SmC^*_A phase in the material. The dielectric studies have been carried out in the frequency range of 1 Hz–35 MHz under planar anchoring conditions of the molecules. The dielectric spectrum of the SmC^*_A phase exhibits three relaxation modes due to the collective as well as individual molecular processes. Relaxation frequencies of these modes lie in the range of kHz–MHz regions. Relative permittivity of the material (at 10 kHz) varies from ~8.8 at 98.8°C to 9.9 at 41.0°C. Maximum tilt of the molecule in the SmC^*_A phase is ~43°C. Spontaneous polarisation, switching time and rotational viscosity have also been determined. The maximum value of P_S is ~439 nC/cm² and switching time is the order of 1–5 millisecond, whereas viscosity is moderate.     

Dipole moments of Flourobenzene and its Mesogenic Derivative in 1,4-Dioxane and 1-Butanol Solutions

Experimental data from dielectric investigations of solutions of flourobenzene (FB) and its mesogenic derivative (1-fluoro-4-(4-pentylcyclohexyl) benzene (FPCHB) in 1,4-dioxane are reported for various mole fractions and temperatures. The molecular dipole moments were determined using the Guggenheim-Debye method in the temperature range of 298.2 to 318.2 K. Both fluorinated compounds show a positive and small temperature coefficient for the effective dipole moment. Variations of the effective dipole moment and correlation factor, g, with mole fraction in these mixtures were investigated using the Kirkwood-Frohlich equation. Dielectric measurements were also carried out on binary mixtures of FPCHB with 1-butanol for various concentrations at 318.2 K. The Kirkwood correlation factor, the Bruggeman factor, and the excess permittivity were determined.     

Simulation studies of dipole correlation in the isotropic liquid phase

The Kirkwood correlation factor g₁ determines the preference for local parallel or antiparallel dipole association in the isotropic phase. Calamitic mesogens with longitudinal dipole moments and Kirkwood factors greater than 1 have an enhanced effective dipole moment along the molecular long axis. This leads to higher values of Δ? in the nematic phase. This paper describes state-of-the-art molecular dynamics simulations of two calamitic mesogens 4-(trans-4-n-pentylcyclohexyl)benzonitrile (PCH5) and 4-(trans-4-n-pentylcyclohexyl)chlorobenzene (PCH5-Cl) in the isotropic liquid phase using an all-atom force field and taking long range electrostatics into account using an Ewald summation. Using this methodology, PCH5 is seen to prefer antiparallel dipole alignment with a negative g₁ and PCH5-Cl is seen to prefer parallel dipole alignment with a positive g₁; this is in accordance with experimental dielectric measurements. Analysis of the molecular dynamics trajectories allows an assessment of why these molecules behave differently.     

2-Acyl(aroyl)-1,1,3,3-tetracyanopropenides: VI. Reaction with hydrogen halides

Reactions of 2-aroyl-1,1,3,3-tetracyanopropenides with hydrogen halides in solvents of low dielectric permittivity result in the formation of 6-amino-2-aroyl-2-halopyridine-3,5-dicarbonitriles. 2-Acyl-1,1,3,3-tetracyanopropenides under similar conditions afford 2-(2-alkylidene-5-amino-4-cyano-2,3-dihydrofuran-3-ylidene)propanedinitriles. In solvents of high dielectric permittivity the result of the reaction depends on the nature of the hydrogen halide and the acyl(aroyl) substituent: With HCl and HBr 2-aroyl-1,1,3,3-tetracyanopropenides form 2-(5-amino-2-aryl-2-halo-4-cyano-2,3-dihydrofuran-3-ylidene)-propanedinitriles, and 2-acyl-1,1,3,3-tetracyanopropenides give 2-(2-alkylidene-5-amino-4-cyano-2,3-dihydrofuran-3-ylidene)propanedinitriles; with HI depending on the reaction conditions and the structure of the acyl substituent 2-(5-amino-2-aryl-4-cyano-2,3-dihydrofuran-3-ylidene)propanedinitriles, 2-(5-amino-4-cyano-2,3-dihydrofuran-3-ylidene) propane-dinitrile, 2-amino-4-(dimethoxybenzyl)-6-iodo-5-cyanonicotinamide, 4-amino-6-iodo-3-oxo-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine-7-carbonitrile, or 4-amino-6-iodo-3-oxo-1-ethylidene-1,3-dihydrofuro[3,4-c]pyridine-7-carbonitrile are obtained.     

Synthesis of Methyl-N-[4-(3-R-amino-2-hydroxypropoxy)phenyl]carbamates

By alkylation of methyl-N-(4-hydroxyphenyl)carbamate with (chloromethyl)oxirane in acetone in the presence of K₂CO₃ methyl-N-[4-(2,3-epoxypropoxy)phenyl]carbamate was prepared. The aminolysis of the latter effected by benzylamine, morpholine, piperidine, and pyrrolidine occurs in keeping with Krasusky rule to afford methyl-N-[4-(3-R-amino-2-hydroxypropoxy)phenyl]carbamates.     

Dielectric properties of binary mixtures of three butanediols with 1,4-dioxane and 2-ethyl-1-hexanol at T = 298.2 K

Experimental results of dielectric investigations for solutions of the three butanediols {2,3-butanediol (2,3BD), 1,3-butanediol (1,3BD), and 1,4-butanediol (1,4BD)}, in 1,4-dioxane (1,4DX) are reported for various mole fractions at T = 298.2 K. Values of relative permittivity were measured at 100 kHz. The molecular dipole moments were determined using Guggenheim method. The variations of effective dipole moment and correlation factor, g, with mole fraction in these materials were investigated using Kirkwood–Frohlich equation. Dielectric measurements were also carried out on binary polar mixtures of the butanediols with 2-ethyl-1-hexanol (2EH) for various concentrations at T = 298.2 K. The Kirkwood correlation factor, the Bruggeman factor, and the excess permittivity were determined.     

Dielectric studies of liquid crystals under high pressure III. Low frequency relaxation process in 4-(trans-4′-n-hexylcyclohexyl)isothiocyanato benzene

Abstract

Dielectric studies of 4-(trans-4′-n-hexylcyclohexyl) isothiocyanatobenzene (6CHBT) were performed in the pressure range 0·1–150 MPa, the frequency range 1 kHz–13 MHz and the temperature range 295–325 K. The temperature and pressure dependencies of the static permittivity ?_0∥ and of the relaxation time τ_∥ are analysed and compared with the analogous data obtained recently for 4-n-pentyl-4′-cyanobiphenyl (5CB) (Parts I and II of this series). Marked differences in the dielectric properties of the nematic phases of the two substances are observed. They are interpreted as a result of varying degrees of molecular association in particular compounds. It is concluded that in the nematic phase of 6CHBT dipole–dipole correlations do not exist or are very weak, whereas for 5CB they are easily broken by a relatively low pressure.     

Dielectric,viscous and elastic properties of nematogenic 1-(4- trans -propylcyclohexyl)-2-(4-cyanophenyl)ethane

This paper presents the results of measurements of the static and dynamic electric permittivity, the shear viscosity of a freely flowing sample, and the splay and bend elastic constants for 1-(4-trans -propylcyclohexyl)-2-(4-cyanophenyl)ethane (C3H7-CyHx-CH2CH2-Ph-C=N) (3CCPE). The static permittivity of the isotropic phase shows pre-nematic critical behaviour which is discussed in the frame of the fluid-like model of Mukherjee. From the temperature dependence of the dielectric relaxation time (corresponding to the molecular rotation around the short axis) and the shear viscosity, the strength of the nematic potential and the effective length of the 3CCPE molecule (in the isotropic phase), were estimated. The splay and bend elastic constants were determined from the voltage dependence of the capacitance of a planar nematic cell.     

Mesogenic 4-acryloyloxy- and 4-(2,3-epoxypropoxy)phenyl 4-alkoxybenzoates

Procedures were developed which made it possible to synthesize in good yields homologs of 4-acryloyloxyphenyl 4-alkoxybenzoates (C₃, C₅, C₇, C₈) and of 4-(2,3-epoxypropoxy)phenyl 4-alkoxybenzoates (C₅, C₇). The substituted phenylbenzoates obtained exhibit the enantiotropic nematic mesomorphism in a sufficiently wide temperature range. The studied compounds have absorption maxima in the near UV region and a high temperature of decomposition beginning.     

Dipole Moment Studies of n-butanol,i-butanol and t-butanol with Chlorobenzene Complexes

Abstract

The dipole moments of H-bonded complexes of n-butanol, i-butanol and t-butanol with chlorobenzene in benzene were investigated from dielectric measurements at 455 kHz and at temperature 303.16 K. The dipole moment of the complex (μab), interaction dipole moment (Δμ) and induced polarization (Pab) for thermodynamically most favoured geometry of 1:1 complexes in these systems were determined. The results shows that the complexation is due to charge redistribution effect in all cases studied and the tendency of complex formation is maximum in n-butanol system.     

Novel approach to relaxation data analysis in polyhydric alcohols

In this paper the experimental data on dielectric permittivity of 1,3-, 1,4- and 2,3-butanediols within the frequency range from 1 MHz to 36 GHz and the temperature range from 283 to 423 K were analyzed. The correlation between relaxation parameters of the Davidson-Cole equation and molecular structure of the investigated butanediols was established. Values of average dipole moments of molecular clusters, 〈μ_c〉, were calculated according to the Dissado-Hill cluster theory. The dependence of 〈μ_c〉 on energy characteristics of the working model was revealed and discussed in details.     

Dielectric studies of a 5-n-alkyl-2-(4'-isothiocyanatophenyl)- 1,3-dioxane (nDBT) homologous series (n=4-10)

The results of dielectric studies of seven members of a 5-n-alkyl-2-(4'-isothiocyanatophenyl)- 1,3-dioxane (nDBT) homologous series (n=4-10) in the isotropic and smectic A phases are presented. The complex dielectric permittivity, epsilon* (nu) = epsilon'(nu) - iepsilon' (nu), was measured with the aid of two experimental set-ups: an impedance analyser (10kHz-13 MHz) and a dielectric time domain spectrometer (TDS, 10 MHz-4 GHz). This allowed two main relaxation processes in both the phases studied to be separated: the low frequency (l.f.) process connected with molecular reorientations around the short axes, and the high frequency (h.f.) process connected with the rotations around the long axes. The measured dielectric increments enabled us to estimate the value and direction of the dipole moment of the nDBT molecules. The l.f. relaxation process in the isotropic and smectic A phases of the nDBT compounds exhibits some peculiar features which distinguish the materials from other similar substances. The observed decrease of the relaxation times and activation enthalpy with increasing n is discussed in relation to the molecular arrangements in the smectic layers.     

Dielectric studies of the 4-n-alkyl-4'-thiocyanatobiphenyl (nBT) homologous series (n=2-10) in the isotropic and E phases

Results of the dielectric studies of nine members of the nBT (4-n-alkyl-4'-thiocyanatobiphenyl, n= 2-10) homologous series in the crystal E (E) and isotropic (I) phases are presented. The dependence of the static permittivity ?_s in the isotropic phase, the longitudinal relaxation times τ_is and τ_∥, and the activation enthalpies ΔH _is and ΔH _∥ on the number of carbon atoms in the alkyl chain n are analysed. A considerable increase in the retardation factor g= τ_∥/τ_is with decreasing n is observed. The results are compared with those obtained for similar two-ring homologous series. The parameters characterizing the molecular rotations around the short axis in the E phase (τ_∥ and ΔH _∥) indicate a hardening of this solid-like phase with shortening of the alkyl chain.     

Study of molecular interactions in the polar binary mixtures of N-methyl aniline and alcohols,using excess dielectric and thermodynamic parameters

Molecular interactions between the polar systems N-methyl aniline and alcohols (propan-1-ol/propan-2-ol) for various mole fractions at different temperatures are studied by determining the dielectric permittivity using LF impedance analyzer, Microwave bench and Abbe’s refractometer in radio, microwave and optic frequency regions respectively. The dipole moment, excess dipole moment, excess Helmholtz energy, excess permittivity, excess inverse relaxation time and excess thermodynamic values are calculated using experimental results. The optimized geometry, harmonic vibrational wave numbers and dipole moments of pure and equimolar binary mixtures have been calculated theoretically from the ab initio Hartree–Fock (HF) and Density Functional Theory (DFT – B3LYP) methods with 6-31+G¹ and 6-311+G⁷ basis sets using Spartan 08 modelling software. Conformational analysis of the formation of hydrogen bond in the equimolar binary mixture systems of N-methyl aniline and alcohols (propan-1-ol/propan-2-ol) is supported by experimental FT-IR spectra. The calculated wave numbers and dipole moments agree well with the experimental values. Further, the correlations among the parameters are discussed in detail.     

Improved mesophase stability of benzoxazole derivatives via dipole moment modification

By modifying the molecular dipole moments with lateral monofluorine substituent, improved mesophase stabilities were obtained for novel benzoxazole derivatives, 2-(4?-alkoxy-3-fluorobiphenyl-4-yl)-benzoxazole liquid crystals (coded as nPPF(3)Bx). The series of nPPF(3)Bx with lateral monofluorine substituent ortho to benzoxazole group have larger calculated dipole moments by about 2 D than the corresponding fluorine-substituted analogs (compounds I) with lateral monofluorine ortho to alkoxy group; it is interesting to note that they show lower melting and clearing points but better mesophase stability with wider mesophase ranges for the molecules with both polar (NO₂, Cl) and nonpolar (CH₃, H) terminal groups. Meanwhile, compounds nPPF(3)Bx show greater red-shifted photoluminescence emissions than compounds I, which suggest that π–π interaction between molecules is reinforced by the enhanced dipole–dipole interaction caused by increased dipole moments. These results suggest that modification of the molecular dipole moment is an effective method to improve the mesophase stability of the classical mesogenic compounds.     

Dielectric anisotropy in the nematic phase of 8PCH as a function of temperature and pressure

The dielectric permittivity components, ε_∥ and ε_⊥, in the nematic phase of 8PCH (trans-4-n-octyl(4-cyanophenyl)cyclohexane) were measured at 1 atm as a function of temperature (T), and at two temperatures as a function of pressure (p). A close similarity of the temperature and pressure behaviours of the dielectric anisotropy, δε = ε_∥ - ε_⊥, was established. It is argued that p and T are equivalent quantities in the formation of the nematic state. The well known Maier and Meier equations describe the dielectric parameters under both p = constant and T = constant conditions fairly well.     

Azimine. VI. 1-Alkoxycarbony 1-2,3-dialkyl- und -2,3-diaryl-azimine

Azimines VI: 1-Alkoxycarbonyl-2,3-dialkyl- and -2,3-diarylazimines Alkoxycarbonyl-nitrenes 2 – generated in situ by α-elimination from N-[(4-nitrophenyl)-sulfonyloxy]carbamates 4 – were reacted with six aliphatic and aromatic azo compounds to yield 1-alkoxycarbonyl-azimines 11 (R′ = Alkyl). Thus, (2Z)- or (2E)- 1 -alkoxycarbonyl-2,3-diisopropyl-azimines ( 8 or 9 ) were obtained stereospecifically from (E)- or (Z)-1,1′-dimethylazoethane ( 5 or 6 ) and 1-alkoxycarbonyl -2,3-(cis-1,3-cyclopentylene)-azimines ( 10 ) resulted from 2,3-diazabicyclo[2.2.1]-2-heptene ( 7 ), always using both ethoxy- and methoxycarbonyl-nitrene ( 2a and 2b ). With 2a , (E)-azobenzene ( 14 ) was converted only to a single stereoisomer of 1-ethoxycarbonyl-2,3-diphenyl-azimine ( 17 ) and both stereoisomers of azo(p-toluene) ( 15 or 16 ) reacted to give the same stereoisomer of 1-ethoxycarbonyl-2,3-di(p-tolyl)-azimine ( 18 ).     

瓜环与4,4'-二氨基二苯甲烷衍生物的相互作用

合成了三种长链多芳环多胺基客体, 它们分别由三种醛基吡啶异构体与4,4'-二氨基二苯甲烷形成的Schiff碱还原而成, 并得到¹H NMR以及质谱分析方法表征证实. 以核磁共振技术、紫外吸收光谱分析方法以及滴定¹H NMR方法为研究手段, 对瓜环(cucurbit[n]urils, n＝6～8)分别与三种4,4'-二[N-(吡啶甲基)氨基]二苯甲烷盐酸盐相互作用进行了考察. 实验结果表明, 六元瓜环与三种4,4'-二[N-(吡啶甲基)氨基]二苯甲烷盐酸盐相互作用均形成物质的量之比为2∶1的哑铃型包结配合物; 八元瓜环与三种N,N'-二(N-(吡啶甲基)二苯甲烷盐酸盐相互作用形成以类轮烷结构为主的包结配合物; 七元瓜环与三种N,N'-二(N-(吡啶甲基)二苯甲烷盐酸盐相互作用存在多种模式的竞争.