In-situ monitoring of a film preparation process for hydroxypropyl cellulose cast from isotropic aqueous solution using microdielectrometry

Solid cast films with polydomain textures were prepared on a glass substrate with transparent interdigitated electrodes from an isotropic aqueous solution of hydroxypropyl cellulose via its liquid crystalline phase under the sinusoidal electric field with small amplitude and frequency of 0.05 V µm^-1 and 10⁵ Hz, respectively. The process was monitored using microdielectrometry as well as polarised optical microscopy. The apparent dielectric constant ε_r' and loss factor ε_r' sensitively changed with time depending on the process conditions. On the other hand, the logarithmic relation between ε_r' and ε_r' showed a single curve, when they were normalised by an effective portion of the electrostatic energy density estimated using each solid-film thickness. The conversion to the solid film was estimated during the process based on the concentration dependences of ε_r' and ε_r'. Characteristic times were reported for the onset of the biphasic phase, fully developed cholesteric phase and termination of the process.     

Concentration dependences of dielectric properties at 105 Hz and 106 Hz for aqueous solutions of hydroxypropyl cellulose

The concentration dependences of dielectric properties measured at 10⁵ Hz and 10⁶ Hz are reported for aqueous solutions of hydroxypropyl cellulose. Phase behaviour of the solutions was also observed with a polarizing optical microscope. For solutions with concentrations well above 40 wt %, polydomain textures, including the banded texture, were observed after a prehistory of deformation. No significant discontinuous changes in the dielectric constant, ε_r′, and loss factor, ε_r″, were found at the concentrations around the onset of the isotropic–cholesteric phase transition and in the biphasic region. In contrast, the steeper changes in ε_r′ and ε_r″ were found at the critical concentration for the fully developed cholesteric phase transition with the polydomain textures.     

Molecular alignment of the 4-octyl-4'-cyanobiphenyl liquid crystal filled with SiO2

The molecular dynamics and molecular alignment of the dispersed 4-octyl-4'-cyanobiphenyl (8CB) liquid crystal with 5 wt % of SiO₂ nanosphere particles have been studied using dielectric spectroscopy. The measurements were performed in the frequency range between 10²-10⁷ Hz in the SmA, N and I phases. The results show only one Debye relaxation process at high frequency (10⁵-10⁷ Hz). In the bulk material, activation energies of 40, 58 and 63 kJ mol^-1 were determined for the SmA, N and the I phases, respectively. In the dispersed sample, the activation energies were found to be 52, 76 and 81 kJ mol^-1, respectively. These results are compared with the available data in the literature. The reversible electromechanical response of the dispersed sample under the influence of an applied a.c. electric field was investigated in the SmA, N, and I phases.     

The octant rule: XXIII. antioctant effects in γ,δ -unsaturated ketones.

The and -benzyl derivatives (1 and 2, respectively) of (+)-camphor have been synthesized and are found to exert a strong influence on the circular dichroism n→π^* Cotton effects: 1: Δε³⁰¹_max -0.36 (n- heptane) and 2: Δε³⁰²_max +3.22, relative to camphor: Δε³⁰⁴_max +1.8 (n-heptane). Evidence for electric dipole transition moment coupling in these γ, δ -unsaturated systems is found in the n→π^* UV: 1: ε²⁹¹_max 84 (n-heptane) and 2: ε²⁸⁵_max 303, relative to camphor: ε²⁹⁰_max 25.     

Collective dynamic modes in ferroelectric liquid crystal-aerosil dispersions

The influence of the concentration of hydrophilic aerosil particles on the collective dynamic modes of the ferroelectric liquid crystal S-(-)-2-methylbutyl 4-n-nonanoyloxybiphenyl-4'-carboxylate near the SmA-SmC* phase transition is investigated by means of dielectric spectroscopy in the frequency range 10^-2-10⁷ Hz. For aerosil densities ρ_s = 0.025, 0.05, 0.08 and 0.15 g cm^-3 considerable changes in the dielectric intensities of Goldstone and soft modes are observed. The characteristic frequency of the Goldstone mode slightly increases with increasing concentration of aerosil. The frequency degeneracy occurring in the SmA-SmC* phase transition is lifted in the presence of aerosil and an increase in the frequency gap is observed. Complete disappearance of the Goldstone mode at ρ_s = 0.20 g cm^-3 occurs, along with significant broadening of the soft mode. The results are interpreted as an effect of structure, surface interactions and length scale of the helix in disordered confinement.     

The effect of polymer chain length on the thermodynamics of acrylate/cyanobiphenyl mixtures

The effect of polymer molecular mass on the phase behaviour and solubility limits of polymer/liquid crystal mixtures is studied for blends of poly(methyl methacrylate) (PMMA) and the small-molecule liquid crystal, 4'-octyl-4-biphenylcarbonitrile (8CB). The phase diagrams from optical microscopy show a limit to the effect of increasing polymer molecular mass. The Flory-Huggins theory (FH) for polymer solutions is used to extract the interaction parameter, χ, from the phase diagrams. The initial FH fits are performed with the assumption that χ is independent of polymer molecular mass, but result in poor correlation to the microscopy data. When χ is allowed to scale with M _w, however, the FH fits are consistent with the limiting molecular mass behaviour. This result represents, to our knowledge, the first time that this scaling behaviour has been observed in polymer/liquid crystal blends. The solubility limit, β, of 8CB in PMMA for each polymer molecular mass is also determined and, when compared with the results of previous studies, support the concept that β is independent of both polymer composition and molecular masses when the polymer molecular mass exceeds ca. 5×10⁵ g mol^-1.     

Substantial velocity dependence of rotationally inelastic collision cross sections in Li2—Xe

A Doppler-based velocity selection technique has been used to measure the relative velocity dependence of the cross sections σ_ji,Δ(ν_r) for rotationally inelastic collisions from level j_i to j_i + Δν₁ = 8,22,42) in ⁷Li^*₂ A ¹Σ⁺_u)—Xe. The σ_jν^±2(ν_r) are strongly attenuated at a smaller ν_r by “torque averaging” due to molecular rotation; in contrast, for large |Δ|, σ_jiΔ = ν_r⁻ⁿ (1 n 2). An empirical intermolecular potential which reproduces these types of behavior for 3-D classical trajectories is exhibited.     

Collective and molecular dynamics in low molar mass and polymeric ferroelectric liquid crystals

By use of a novel sample preparation technique, it is possible to measure with one sample cell the collective and molecular dynamics (10^-1 Hz-10⁹ Hz) of macroscopically (in bookshelf geometry) oriented ferroelectric liquid crystals. Below 10⁶ Hz, two ferroelectric modes, Goldstone- and soft-mode, are observed, being assigned to fluctuations of the phase and amplitude of the helical superstructure respectively. Between 10⁶ and 10⁹ Hz, one dielectric loss process exists, the β-relaxation which originates from the librational motion (hindered rotation) of the mesogen around its molecular long axis. This process does not split or broaden at the non-ferroelectric-ferroelectric phase transition and it has an Arrhenius type temperature dependence. In comparing a racemic mixture with a chiral sample, it performs a similar frequency and temperature dependence. The experimental findings for the β-relaxation are in qualitative contrast to the predictions of the (generalized) Landau expansion of the free energy at the non-ferroelectric-ferroelectric phase transition. The experiment also leads to a modified understanding for the molecular origin of ferroelectricity in FLCs.     

Dielectric relaxation in bulk and cylindrically confined octylcyanobiphenyl (8CB)

The dielectric relaxation spectrum over the frequency range 10² to 1.8×10⁹ Hz of 4-octyl-4'-cyanobiphenyl, 8CB, in bulk and confined to 200 nm diameter cylindrical pores is reported. We used matrices with parallel cylindrical pores, obtaining different alignments of the molecular director depending on the treatment. Results show that there are two relaxations in the isotropic phase and in the mesophases for parallel alignment and three for perpendicular alignment. The molecular origin of theses modes and the effect of the confinement on their dynamics are discussed. To compare properly the results for bulk and confined 8CB, a re-scaling of the experimental data is proposed.     

Influence of hydrophilic and hydrophobic aerosil particles on the molecular modes in the liquid crystal 4-n-pentyl-4'-cyanobiphenyl

Dielectric spectroscopy in the frequency range 10⁶-10⁹ Hz was applied to investigate the influence of hydrophilic and hydrophobic aerosil particles on molecular processes in the liquid crystal 4-n-pentyl-4'-cyanobiphenyl. The dynamics of the molecular process in the isotropic phase is non-Arrhenius; it weakly depends on the aerosil density and shows critical temperature dependence of the activation energy near the isotropic-nematic phase transition. The relaxation rate of the process related to the hindered rotation of the molecule around its molecular short axis (slower process) follows an Arrhenius law over about thirty degrees in the nematic range (except close to the phase transition) with an activation energy comparable to the bulk and is almost independent of the aerosil density. The relaxation rate of the process originating from the fluctuation of the molecular long axis around the director (librational mode, faster process), however, follows the Vogel-Fulcher-Tammann law. With increasing disorder achieved by increasing the aerosil density, the relative dielectric strength of the librational mode increases in comparison with the bulk. The relaxation frequency of the slower process increases but that of the faster process decreases with increasing aerosil density. Both these effects are less pronounced for hydrophobic than for hydrophilic aerosils.     

Monodentate and bidentate trifluoroacetato ligands in bis(trifluoroacetato)-(N-methyl-meso-tetraphenylporphyrinato)thallium(III)—a new dynamic 4:3 piano stool seven-coordinate geometry

The crystal structure of bis(trifluoroacetato)-(N-methyl-meso-tetraphenylporphyrinato) thallium(III), Tl(N---Me---tpp)(CF₃CO₂)₂ (2), was established and the coordination sphere around the Tl³⁺ ion is described as 4:3 tetragonal base–trigonal base piano stool seven-coordinate geometry in which the two cis CF₃CO₂ ⁻ groups occupy two apical sites. The plane of the three pyrrole nitrogen atoms [i.e. N(2), N(3) and N(4)] strongly bonded to Tl³⁺ is adopted as the reference plane 3N. The pyrrole N(1) ring bearing the methyl group [i.e. C(45)H₃] is the most deviated one from the 3N plane making a dihedral angle of 23.3° whereas smaller angles of 9.9, 2.7 and 4.7° occur with pyrroles N(2), N(3), and N(4), respectively. Because of the larger size of the thallium(III) ion, Tl is considerably out of the 3N plane; its displacement of 1.02 Å is in the same direction as that of the two apical CF₃CO₂ ⁻ ligands. The intermolecular trifluoroacetate exchange process for 2 in CD₂Cl₂ solvent is examined through ¹⁹F and ¹³C NMR temperature-dependent measurements. In the slow-exchange region, the CF₃ and carbonyl (CO) carbons of the CF₃CO₂ ⁻ groups in 2 are separately located at δ 114.3 [¹J(C–F)=290 Hz, ³J(Tl–C)=411 Hz] and 155.1 [²J(C–F)=37 Hz, ²J(Tl–C)=204 Hz], respectively, at −106 °C. In the same slow-exchange region, the fluorine atoms of 2, Tl(N---Me---tpp)(CF₃CO₂)⁺ and the free CF₃CO₂ ⁻ are located at δ −73.76 [⁴J(Tl–F)=44 Hz], −73.30 [⁴J(Tl–F)=22 Hz], and −76.15 ppm at −97 °C, respectively.     

Structural evolutions of the n-heneicosane and n-tricosane molecular alloys at 293 K

A structural study of odd-numbered n-alkane (C_n) binary mixtures (C₂₁ : C₂₃) was carried out on powder samples using a Guinier-de Wolff camera with increasing concentration of n-C₂₃ at 293 K.

Despite the reports in the literature, these molecular alloys do not form an orthorhombic continuous homogeneous solid solution to C₂₁ from C₂₃ at “low temperature”. Instead, as already observed in two even-numbered C_n systems, X-ray diffraction results show the existence of seven solid solutions as the molar concentration of C₂₃ increases: four terminal solid solutions, denoted β₀(C₂₁)β₀(C₂₃), isostructural with the “low temperature” phase of pure C₂₁ and C₂₃ (Pbcm), β′₀(C₂₁) and β′₀(C₂₃), identical to the phase β′₀ which appears in pure C₂₃ above the δ transition, and three orthorhombic intermediate solid solutions, designated β″₁, β′₁ and β″₂.

On the basis of powder X-ray photographs, the phases β″₁ and β″₂ (C₂₁ : C₂₃) are indistinguishable, and they are isostructural with the intermediate solid solution β″ of the even-numbered C_n binary systems (C₂₂ : C₂₄) and (C₂₄ : C₂₆). The phase β′₁(C₂₁ : C₂₃) is also isostructural with the two indistinguishable intermediate solid solutions β′₁ and β′₂ of the molecular alloys (C₂₂ : C₂₄) and (₂₄ : C₂₆).

From this study and our other laboratory results, the sequences of appearance of the solid solutions and the structural identities between these phases are established at “low temperature” for all the binary molecular alloys of consecutive C_n (odd-odd, even-even or odd-even: 19 < n < 27) when increasing the solute concentration.     

Structures of propionaldehyde, butyraldehyde, and pivalaldehyde complexes of the chiral rhenium fragment [(η-C5H5)Re(NO)(PPh3)]

The crystal structures of propionaldehyde complex (RS,SR)-(η⁵-C₅H₅)Re(NO)(PPh₃)(η²-O=CHCH₂CH₃)]⁺ PF₆⁻ (1b⁺ PF₆^s−; monoclinic, P2₁/c (No. 14), a = 10.166 (1) Å, b = 18.316(1) Å, c = 14.872(2) Å, β = 100.51(1)°, Z = 4) and butyraldehyde complex (RS,SR)-[(η⁵-C₅H₅)Re(NO)(PPh₃)(η²-O=CHCH₂CH₂CH₃)]⁺ PF₆⁻ (1c⁺PF₆⁻; monoclinic, P2₁/a (No. 14), a = 14.851(1) Å, b = 18.623(3) Å, c = 10.026(2) Å, β = 102.95(1)°, Z = 4) have been determined at 22°C and −125°C, respectively. These exhibit C O bond lengths (1.35(1), 1.338(5) Å) that are intermediate between those of propionaldehyde (1.209(4) Å) and 1-propanol (1.41 Å). Other geometric features are analyzed. Reaction of [(η⁵-C₅H₅)Re(NO)(PPh₃)(ClCH₂Cl)]⁺ BF₄⁻ and pivalaldehyde gives [(η⁵-C₅H₅)Re(NO)(PPh₃)(η²-O=CHC(CH₃)₃)]⁺BF₄⁻ (81%), the spectroscopic properties of which establish a π C O binding mode.     

Synthesis, structure and hydrogenation catalytic activity of [Ru3(μ3,η-ampy)(μ,η:η-PhC=CHPh)(CO)6(PPh3) (Hampy = 2-amino-6-methylpyridine)

The compound [RU₃(μ₃,η²- -ampy)(μ₃η¹:η²-PhC=CHPh)(CO)₆(PPh₃)₂] (1) (ampy = 2-amino-6-methylpyridinate) has been prepared by reaction of [RU₃(η-H)(μ₃,η²- ampy) (μ,η¹:η²-PhC=CHPh)(CO)₇(PPh₃)] with triphenylphosphine at room temperature. However, the reaction of [RU₃(μ-H)(μ₃, η² -ampy)(CO)₇(PPh₃)₂] with diphenylacetylene requires a higher temperature (110°C) and does not give complex 1 but the phenyl derivative [RU₃(μ₃,η²-ampy)(μ,η ¹:η² -PhC=CHPh)(μ,-PPh₂)(Ph)(CO)₅(PPh₃)] (2). The thermolysis of complex 1 (110°C) also gives complex 2 quantitatively. Both 1 and 2 have been characterized by0 X-ray diffraction methods. Complex 1 is a catalyst precursor for the homogeneous hydrogenation of diphenylacetylene to a mixture of cis- and trans -stilbene under mild conditions (80°C, 1 atm. of H₂), although progressive deactivation of the catalytic species is observed. The dihydride [RU₃(μ-H)₂(μ ₃,η²-ampy)(μ,η¹:η²- PhC=CHPh)(CO)₅(PPh₃)₂] (3), which has been characterized spectroscopically, is an intermediate in the catalytic hydrogenation reaction.     

MRD CI study on the low-lying states of AlP

Large-scale MRD CI calculations assign to AlP the ground state X ³Σ⁻ (9σ²3π²) and a close-lying state 1 ³Π (9σ3π³) (T_e = 0.08 eV). Up to transition energies of 2.0 eV, other states are described by the configurations 9σ3π³ (1¹Π), 8σ²3π⁴ (1 ¹Σ⁺), 9σ²3π² (1 ¹Δ and 2 ¹Σ⁺) and 9σ3π²4π (1 ⁵Π). The 2 ³Π state, located at ≈ 2.30 eV, shows a shallow double minimum. Numerous perturbations are expected to induce predissociation upon 2 ³Π. Multiplets arising from the occupation 8σ²3π³4π are clustered in the 3.25–3.50 eV region. Quintet states with the configuration 8σ9σ3π³4π are bound, with T_e values (in eV) of 3.80 (1 ⁵Σ⁺), 4.44 (1 ⁵Δ) and 4.88 (3 ⁵Σ⁻), respectively. The 9σ → 4s Rydberg members ⁵Σ⁻ and ³Σ⁻ lie in the 4.58–4.72 eV energy region. The first ionization potential (ionization to X⁴Σ⁻ of AlP⁺, 9σ → ∞) is estimated to be 7.65 eV. Ionization to the 1 ²Σ⁻ and 1 ²Π states of AlP⁺ is suggested to occur between 8.0 and 8.8 eV. The dipole moments of X ³Σ⁻, 1 ¹Δ and 2 ¹Σ⁺ are close to 1.0 D, whereas the 1 ¹Σ⁺ state has μ = 3.49 D; 1 ³Π and 1 ¹Π have dipole moments from 2.45 to 2.91 D. All low-lying states show a polarity Al⁺P⁻. Finally, the electronic structure and transition energies of AlP are compared with those of the isoelectronic species BN, AIN, and SiP⁺.     

The system CePO4–K3PO4

The phase diagram of the system CePO₄–K₃PO₄ has been determined based on investigations by differential thermal analysis, X-ray powder diffraction, IR spectroscopy and optical microscopy. The system contains only one intermediate compound K₃Ce(PO₄)₂, which melts incongruently at (1500±20)°C. This compound is stable down to room temperature and exhibits a polymorphic transition at 1180°C. It was confirmed that the low-temperature form β-K₃Ce(PO₄)₂ crystallizes in a monoclinic system, space group P2₁/m with unit cell parameters a=9.579 (5), b=5.634 (6), c=7.468 (5) Å; =γ=90°, β=90.81 (3)°; V=403.083 Å³.     

Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)2}2V4O12]·5H2O and [Ni(phen)3]2[V4O12]·17.5H2O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen₂)₂V₄O₁₂]·5H₂O (1) and [Ni(phen)₃]₂[V₄O₁₂]·17.5H₂O (2). Crystal data: C₄₈H₅₂Cd₂N₈O₂₂V₄ (1), triclinic. a=10.3366(10), b=11.320(3), c=13.268(3) Å, =103.888(17)°, β=92.256(15)°, γ=107.444(14)°, Z=1; C₇₂H₁₃₁N₁₂Ni₂O_29.5V₄ (2), triclinic. a=12.305(3), b=13.172(6), c=15.133(4), =79.05(3)°, β=76.09(2)°, γ=74.66(3)°, Z=1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59° <θ<26.02° and 2.01°<θ<25.01° using the ω-scan technique, respectively. The structure of 1 consists of a [V₄O₁₂]⁴⁻ cluster covalently attached to two {Cd(phen)₂}²⁺ fragments, in which the [V₄O₁₂]⁴⁻ cluster adopts a chair-like configuration. In the structure of 2, the [V₄O₁₂]⁴⁻ cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the [V₄O₁₂]⁴⁻ unit and crystallization water molecules.     

A convenient synthesis of Fe(CO)2(η-S2CNMe2)2 and Fe(η-S2CNMe2)2 from the monodentate dithiocarbamato derivative, [(η-C5H5)(CO)3W(η-SCSNMe2)] and Fe2(CO)9

A high yield synthesis of the carbonyl dithiocarbamato derivative Fe(CO)₂(η²-S₂CNMe₂)₂ and Fe(η²-S₂CNMe₂)₂ by photolysis with visible light of solutions containing Fe₂(CO)₉ or Fe₃(CO)₁₂ and [(η⁵-C₅H₅)(CO)₃W(η¹-SCSNMe₂)] is reported.     

Versatile reactions of a para-bromophenylacetylide iron(II) derivative and X-ray structure of the fluoro analogue. Synthesis of new redox-active organoiron(II) synthons

The synthesis of the new (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,3-(C₆H₄X) (m-2a/2b; X=F/Br) and (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄I) (2c) complexes, as well as the solid-state structure of the known (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄F) (2a) complex are described. The catalytic coupling reactions of the bromo complexes with various alkynes were next investigated. Starting from the known (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄Br) complex (2b), the synthesis of the (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄)---CC---H complex (6d) and of the corresponding silyl-protected precursors (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄)CC---SiR₃ (6b/6c; R=ⁱPr/Me) are reported. By use of lithium---bromine exchange reactions on 2b, the silyl- (7a; E=Si; R=Me) and tin- (7b–7d; E=Sn; R=Me, Bu, Ph) substituted analogues (η²-dppe)(η⁵-C₅Me₅)Fe---CC---1,4-(C₆H₄)ER₃ are also isolated. The spectroscopic and electrochemical characterisations of all these new Fe(II)/Fe(III) redox-active building blocks are presented and the electronic substituent parameters for the “(η²-dppe)(η⁵-C₅Me₅)Fe---CC” group are determined by means of ¹⁹F-NMR.     

High pressure studies of the static permittivity tensor components in the nematic phase of 6CB

The dielectric permittivity tensor components, ε_II and ε_⊥, in the nematic phase of 6CB (4-n-hexyl-4'-cyanobiphenyl) were measured in the pressure range 0.1-130 MPa and the temperature range 12-58°C. The dielectric anisotropy, Δε(p, V, T) = ε_II - ε_⊥, was analysed in isothermal, isobaric and isochoric conditions taking into account the pVT data and the well known Maier and Meier equation. On that basis the nematic order parameter S(p, V, T) was determined. This was used to calculate the parameter Γ relating the interaction potential with the volume (density). Its value Γ = 4.1 agrees very well with other estimates.