Effect of Halide Ions on the Electronic Conductivity in Calcium Borate Glasses

Some halogen-doped calcium borate glasses containing iron have been prepared according to the percentage molar composition [(30 – x) CaO · x CaX₂ · 10 Fe₂O₃ · 60 B₂O₃] and annealed. It is found that the conduction in the semiconducting glasses is mainly due to electronic conduction. The results show that the halide ions may be introduced as modifiers for CaX₂ concentration < 10 mol% (X >= F, Cl, and Br) but they are network formers at CaX₂ > 10 mol%. It is proposed that at 10 mol% the network structure for all glasses seems to be the same. The dependence of resistivity on the halide ions concentration as well as the slight variation of activation energies, could be explained on the basis of electron-lattice interaction. Mathematical expressions for fitting and describing the dependence of resistivity on CaX₂ concentration are deduced and formulated by the following equations: ϱ = ϱ₀ exp [± ac(1 – bc)] and ϱ ϱ= ±₁₀ exp [± a′c(1 – b′c)] for the two regions around the critical concentration.     

Dielectric Anisotropy and the Order Parameter of HXBBA

Abstract

Measurements of dielectric anisotropy (Δ?), refractive indices (n _e , n _o), birefringence (Δn) and density (ρ) have been made in the nematic and smectic phases of N(-p-hexyloxybenzylidene)-p-butylaniline (HXBBA). The results indicate that the various transitions are of the first order type except smectic B-smectic G, which may be a second order transition. The order parameter S has been determined using the isotropic internal field model (Vuks approach) and the anisotropic internal field model (Neugebauer's approach) and both the values agree fairly well. The dielectric anisotropy (Δ?) increases strongly in the smectic phases whle S increases only slowly. It is interpreted by an increase of dipole-dipole correlations.     

Phase transitions from density and order parameter from polarisabilities in symmetric dimeric liquid crystals

As a part of our systematic studies on liquid crystal dimers, we present in this article the nature of phase transitions across isotropic–nematic and nematic–smectic-A exhibited by DLCs, α,ω-bis-(4-n-alkylaniline benzylidene-4?-oxy) alkanes. Further, the orientational order parameter in the nematic phase of these DLCs are estimated from the molecular polarisabilities calculated using the experimental refractive indices and density results. The molecular polarisabilities α_e and α_o are obtained for the compounds using the above results for both Vuks and Neugebauer local field models applicable to nematic liquid crystal. α_e and α_o calculated in this way are used to obtain Δα. The polarisability anisotropy in the perfect order (absolute K) is calculated semi-empirically using the δ-function model developed by Lippincott et al. and molecular vibration method. The values of polarisability anisotropy for both local electric field models differ significantly. No criterion is known to decide which value is correct. To avoid the determination of uncertain α and Δα values considering different local field models, a simple procedure developed by Kuczynski et al. was used for evaluation of S, based solely on birefringence δn = (n_e-n_o) and this value of S is compared with those obtained from field models.     

Structure of the undecahydrodecaborate anion B10H

The crystal structures of [Ph ₃PCH₂ Naph]B₁₀H₁₁(I) and [Ph ₃PEt]₂B₁₀H₁₀ (II) are studied (110 K and room temperature, R = 0.0673 and 0.0609 for 4176 and 953 observed reflections in I and II, respectively). It is unambiguously determined that protonation of the B₁₀H ₁₀ ²⁻ anion proceeds at one of the faces of the apical belt and results mainly in a significant lengthening of the edges of the centered face [B_e-B_e, 1.948(4) Å; B_a-B_e, 1.770(5) Å and 1.787(5) Å]. __________ Translated from Kristallografiya, Vol. 49, No. 5, 2004, pp. 855–859. Original Russian Text Copyright ? 2004 by Polyakova, Mustyatsa, Zhizhin, Kuznetsov.     

The Internal Field Parameters for Liquid Crystals

This paper presents calculations of the internal field constants γ_e for four homologous liquid crystal materials in their nematic and crystalline phases. We find that for the nematic phase, the γ_e ～ S ₂ curve is nearly a straight line for each compound. When one extrapolates the straight line to S ₂ = 1, the corresponding γ_e value is nearly equal to γ∥, the crystalline internal field constant. The birefringence data used are those reported by Somashekar et al.⁴ The four compounds studied are:

(1) p(p'-ethoxyphenylazo)phenyl valerate;

(2) p(p'-ethoxyphenylazo)phenyl hexanote;

(3) p(p'-ethoxyphenylazo)phenyl heptanoate;

(4) p(p'-ethoxyphenylazo)phenyl undecylenate.     

Determination of Nitrogen Concentration in GaP Epitaxial Layers by Two Independent Methods

The nitrogen concentration in GaP is determined by optical absorption in the A-line at T = 77 K. The concentration of the isolated nitrogen atoms is given for T = 77 K by the modified LIGHTOWLERS' relation [N_A] cm⁻³ = 8.2 · 10¹⁴ phα_max, where α is measured in cm⁻³, h in meV. p is a dimensionless line shape factor. It is shown that at higher N concentrations considering only the A-line absorption the impurity density is underestimated because the nitrogen atoms included in NN_i pairs give no contribution to the absorption. The measurements have been made in the range from [N] = 5 · 10¹⁶…︁ 10¹⁹ cm⁻³ in layers grown by vapour phase epitaxy. The results are compared with nitrogen concentrations obtained by precision lattice parameter measurements. The change of the lattice parameter is calculated using VEGARD's law. The good agreement between the nitrogen densities obtained by two different independent methods reveals (i) that the LIGHTOWLERS' calibration factor is valid also at higher N-concentrations and (ii) that the nitrogen atoms are predominantly incorporated into P-lattice sites.     

Syntheses,crystal structures and properties of Cd(II) and Ag(I) complexes based on 2-p-methylphenyl-5-(2-pyridyl)-1,3,4-thiadiazole

Abstract

Complexes of [CdL₂(NO₃)₂]·1.5H₂O and [Ag₂(μ-L)₂(NO₃)₂] were synthesized by the reactions of 2-p-methylphenyl-5-(2-pyridyl)-1,3,4-thiadiazole (L) with Cd(NO₃)₂·4H₂O and AgNO₃, respectively. Their structures were determined by single crystal X-ray diffraction. The photophysical property and thermal stability were characterized by FT???IR, UV???Vis absorption, fluorescence, and thermogravimetric analysis (TGA). Both complexes belong to the triclinic system with space group p???1. The central metal of [CdL₂(NO₃)₂]·1.5H₂O has a distorted octahedral geometry [CdN₄O₂], while two central Ag(I) atoms of [Ag₂(μ-L)₂(NO₃)₂] exhibit distorted tetrahedral geometries [AgN₃O].     

Dispersive power and crossover temperature,TCO, of two polar nematic liquid crystals in the visible spectral region

Refractive index studies are carried out on two highly polar liquid crystals: 1. N-(p-n-methoxy benzylidene)-p-amino benzonitrile, PmBAB, 2. N-(p-n-ethoxy benzylidene)-p-amino benzonitrile, PeBAB. The experimental investigations are carried out in the visible region at four different wavelengths, namely, 633, 589, 546 and 436 nm. The two compounds exhibit only the nematic liquid crystalline phase in between the isotropic and crystalline solid. The dispersive power ω is estimated for two consecutive wavelengths for the case of <n>, n_e and n_o for different wavelengths and found to be constant with temperature. Further the temperature gradients of n_e and n_o are estimated, and the crossover temperature is obtained using dn_o/dT for all the wavelengths.     

An Organoplatinum(II) Complex of a Bitopic,Propylene-linked Bis(pyrazolyl)methane Ligand

Abstract The reaction of the third-generation, bis(pyrazolyl)methane ligand 1,1,5,5-tetra(1-pyrazolyl)pentane, [CH(pz)₂]₂(CH₂)₃ (pz = 1-pyrazolyl), with the dimer [Pt(p-tolyl)₂(μ-SEt₂)]₂ yields the complex {μ-[CH(pz)₂]₂(CH₂)₃}[Pt(p-tolyl)₂]₂. The complex crystallizes in the space group P with unit cell dimensions a = 11.9461(5) ?, b = 12.1475(5) ?, c = 16.0665(7) ?; α = 102.424(1)°, β = 104.413(1)°, γ = 102.140(1)°. The platinum centers adopt a square planar coordination geometry where each bis(pyrazolyl)methyl group binds in a cis bidentate fashion. Index abstract The complex {μ-[CH(pz)₂]₂(CH₂)₃}[Pt(p-tolyl)₂]₂ (pz = 1-pyrazolyl) has been prepared by the reaction between the bis(pyrazolyl)methane ligand [CH(pz)₂]₂(CH₂)₃ and [Pt(p-tolyl)₂(μ-SEt₂)]₂. Daniel L. Reger*, Russell P. Watson, and Mark D. Smith Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, USA,reger@mail.chem.sc.edu      

Preparation and some properties of thallium orthothioarsenate single crystals

Growing of large (Ø 25–30 mm, L = 50–60 mm) optically homogenous single crystals of Tl₃AsS₄ using the Bridgman-Stockbarger method is described. Tl₃AsS₄ is orthorhombic (Pnma), a = 8.85 ± 0.03, b = 10.86 ± 0.03, c = 9.18 ± 0.03 Å; z = 4; ϱ_x = 6.15 g · cm⁻³; ϱ_p = 6.15 ± 0,03 g · cm⁻³, T_m = 424 ± 3°C, Moh's hardness = 3, microhardness and ultrasonics velocity along x, y, z are 65–85 kg · mm⁻² and 2.16 – 2.37 · 10⁵ cm · sec⁻¹, respectively. The crystals possess perfect cleavage plane (010). Their transparency range is 0.6–12 microns. – Unsuccessful attempts to obtain Tl₃AsS₄ and its alloys in the vitreous state were taken. The possibilities of glass formation and boundaries of the vitreous region in the system Tl–As–S based on the characteristic features of the melt forming structural units are analyzed.     

The coprecipitation of magnesium aluminium hydroxocarbonate powders from aqueous solution: Precipitate compositions and coprecipitation mechanisms

Magnesium aluminium hydroxocarbonate hydrates were coprecipitated from mixed metal nitrate solutions, at total C_M = 0.2 M and Mg/Al₂ = 1 ratio, with four sodium hydrogen carbonate-sodium carbonate solutions (of pH 8.1 to 11.5) at ambient temperature. The course of precipitation was monitored by potentiometric (pH) titration, and the compositions of the primary and final precipitates were determined by chemical analysis, infrared spectrophotometry and X-ray diffraction. Precipitation generally occurred through three stages, primary precipitation (of low CO₃ aluminium hydroxocarbonates) at low pH with evolution of carbon dioxide, their dissolution by complexing to form hydroxocarbonatoaluminate anions and then secondary precipitation of the final coprecipitate at higher pHs. The final product from coprecipitation by sodium hydrogen carbonate solution (pH 8.1) was mainly the magnesium hydroxocarbonatoaluminate ‘MAHC I’; the final products from coprecipitation by sodium hydrogen carbonate-sodium carbonate solutions (pH 9.4 and 10.3) were ‘MAHC I’/‘MAHC II’ mixture and ‘MAHC II’/‘MAHC I’ mixture whereas the final product from coprecipitation by sodium carbonate solution (pH 11.5) was a complex mixture if ‘MAHC II’ with ‘MAHC I’ and ‘MAHC III’;

• ‘MAHC I’ was probably Mg₂[Al₄(OH)₁₀(CO₃)₃] · hH₂O,
• ‘MAHC II’ was probably Mg[Al₂(OH)₄(CO₃)₂] · h H₂O whereas
• ‘MAHC III’ was probably Mg[Al₂(OH)₆CO₃] · h H₂O.

     

The Coprecipitation of Zinc Aluminium Hydroxide Powders from Aqueous Solution with Sodium Hydroxide: Precipitate Compositions and Coprecipitation Mechanisms

Zine aluminium hydroxides were coprecipitated from different mixed metal cation solutions, at C_{M tot} = 0.1 M and at Zn/Al₂ ratios from 1 to 4, with sodium hydroxide solution. The coprecipitations were monitored by potentiometrie (pH) titration and the final coprecipitate compositions were examined by chemical analysis, infra-red spectrophotometry and thermal analysis. Generally, microcrystalline aluminium hydroxide was first precipitated at pH about 4; this then partially redissolved on further addition of sodium hydroxide (to form hydroxoaluminate anion) and zinc aluminium hydroxide coprecipitates were formed continuously at pHs from 5.5–6 to above 9. Their compositions were similar to the magnesium hydroxoaluminate coprecipitated from magnesium aluminium solutions. At Zn/Al₂ ratio = 1, the main phase was probably Zn(H₂O)_n [Al(OH)₄]₂; at Zn/Al₂ ratio = 2, the main phase was probably Zn₂(H₂O)_n [Al₂(OH)₁₀], whereas at Zn/Al₂ ratio = 4, the main phase was probably Zn(H₂O)_n(OH)₄[Al₂(OH)₁₀].     

Synthesis and structural characterization of 5,6,15,16-tetradehydrobenzo[a]phenanthro[9, 10-e]cyclooctene,C24H12

A benzo-phenanthro-fused planar cyclooctatetraene derivative, namely, 5,6,15,16-tetradehydrobenzo[a]phenanthro[9, 10-e]cyclooctene (5) was synthesized in two steps from the known benzo[a]phenanthro[9, 10-e]cyclooctene (6). Compound5 crystallizes in space groupPbam witha=9.828(2),b=19.466(4),c=15.901(3) Å, and Z=8. X-Ray analysis (MoK radiation,R=0.060 for 1233 observed data) has shown that both independent molecules have the same planarC _2v configuration with averaged bond lengths of 1.381(7) and 1.208(7) Å for the phenanthrene C_6a–C_14b bond and the acetylenic CC bond, respectively.¹H and¹³C NMR spectral results of 5 and 5,6,15,16-tetrabromo-5,6,15,16-tetrahydrobenzo[a]phenanthro[9, 10-e]cyclooctene (7) are also presented.     

Synthesis and X-ray diffraction study of [UO<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · 2C<Subscript>12</Subscript>H<Subscript>18</Subscript>O

The compound [UO₂(NO₃)₂(H₂O)₂] · 2C₁₂H₁₈O was synthesized and studied by IR spectroscopy and X-ray diffraction. The structure consists of the neutral island groups [UO₂(NO₃)₂(H₂O)₂], which belong to the crystal-chemical group AB ⁰¹ ₂ M ¹ ₂ (A = UO₂ ²⁺, B ⁰¹ = NO₃⁻, M ¹ = H₂O) of uranyl complexes, and 1-adamantyl methyl ketone molecules. The characteristic features of the association of the complexes [UO₂(NO₃)₂(H₂O)₂] and 1-adamantyl methyl ketone molecules in the crystal structure via hydrogen bonds are considered with the use of Voronoi-Dirichlet polyhedra.     

Birefringence and Order Parameter of Some Alkyl and Alkoxycyanobiphenyl Liquid Crystals

The refractive indices and densities of six liquid crystals—two alkylcyanobiphenyls, three alkoxycyanobiphenyls and one mixture of two alkylcyanobiphenyls have been reported as a function of temperature. The effective polarizabilities α_eand α_o in the nematic phase calculated using the methods due to Neugebauer, Vuks and Saupe and Maier, are found to be appreciably different, though the order parameter S evaluated with those values of (α_e - α_o) are in good agreement. The preference of one method over the other two is discussed.     

Overhauser Shift of the Conduction Electron Spin Resonance in (FA)2PF6 Single Crystals

The shift ΔB _ov of the ESR line due to saturation of the NMR of the hyperfine coupled nuclei (Overhauser shift) was measured for single crystals of the organic conductor (FA)₂PF₆. ΔB_ov , is proportional to [Abar] _tt , being the average hyperfine interaction between the conduction electrons and the protons in resonance, and the dynamic nuclear spin polarization (DNP), respectively. The DNP enhancement factor V was determined for the two orientations of the static magnetic field B _o , perpendicular (V _∥ = 525 ± 40) and parallel (V _∥ = 280 ± 25) to the needle axis a, respectively. The absolute value of the average hyperfine coupling is [Abar]^zz = –(1.16 ± 0.05) Gauss · g_e μ _B . Both, the temperature dependence and the anisotropy of the proton spin relaxation times T ₁ ^p and T ₁ ^p were measured from the time dependence of the Overhauser shift, ΔB_ov (t) after rf-pulses or after switching “on” and “off” the ESR saturation. Within the metallic phase of the crystal the proton relaxation is governed by a Korringa law. The experiments definitely show, that the electron spins, showing up in the ESR are those of the conduction electrons.     

Role of sublattices in the formation of electron density in metal nitrites

The self-consistent valence electron densities of NaNO₂, AgNO₂, and their constituent sublattices are calculated on the basis of the theory of the local-density functional. The quantity characterizing the relation between different sublattices is introduced as the difference density resulting from the subtraction of the densities of the individual sublattices from the total electron density. The role of metal in the formation of electron density is established, and, in particular, it is shown that, in AgNO₂, anionic bonds have the covalent component formed at the expense of the electron density of the cation. It is also shown that, qualitatively, the difference density in NaNO₂ corresponds to the experimental deformation density.     

Polymeric structure of succinatobis(benzimidazole)copper(II) monohydrate

A new complex compound: [Cu(C₇H₆N₂)₂(C₄H₄O₄ H₂O] has been synthesized and its crystal structure investigated by single-crystal X-ray methods. The structure was refined by full-matrix least-squares to giveR=0.031 andR _w =0.038 for 1765 intensities above 3(I). The structure consists of polymeric chains [Cu(C₇H₆N₂)₂(C₄H₂O₄)] parallel to [110] and [¯110], connected by long Cu-H₂O-Cu bonds along [001]. Succinate ions exhibit antiperiplanar conformation and are only bidentate ligands. Interchain interactions by hydrogen bonds and stacking of aromatic ligands are discussed.     

Structure and characterization of hexakis(imidazole) cobalt(II) complexes: [Co(Im)6(OBz)2] and [Co(Im)6(mB)2] (Im = imidazole, OBz = benzoate, mB = p-methoxybenzoate)

The crystal and molecular structures of the complexes of [Co(Im)₆(OBz)₂] and [Co(Im)₆(mB)₂] (Im = imidazole, OBz = benzoate, mB = p-methoxybenzoate) have been determined by X-ray crystallography. The crystal structures are very similar and consist of discrete molecules of [Co(Im)₆(OBz)₂] and [Co(Im)₆(mB)₂], respectively. They both crystallize in the triclinic system, space group the former with lattice parameters a = 7.6934(3), b = 10.4518(5), c = 11.6088(5) Å, = 73.920(1), = 79.023(1), = 73.681(1)°, and Z = 1; the latter with a = 9.8336(3), b = 10.5509(2), c = 10.8889(3) Å, = 61.450(1), = 76.832(1), = 71.157(1)°, and Z = 1. The cobalt(II) ions have octahedral geometry with a CoN₆ chromophore. In the solid state, the complexes all form a three-dimensional network through N—H···O hydrogen bonds. The electronic spectra and IR spectra data are in agreement with the structural data.