Magnetic and transport properties of double distorted perovskites CaCuMn6O12 and CaCu2Mn5O12

Magnetic and transport properties of double distorted perovskites CaCuMn₆O₁₂ and CaCu₂Mn₅O₁₂ are studied in a range 2–300 K. The leading role in magnetism of these compounds belongs to antiferromagnetic exchange interaction of Cu²⁺ in square coordination with Mn³⁺/Mn⁴⁺ in octahedral coordination. The values of saturation magnetization indicate that Mn³⁺ ions in square coordination are coupled ferromagnetically with Mn³⁺/Mn⁴⁺ in octahedral coordination. The colossal magnetoresistance in the pellet samples is due assumingly to intergranular spin-polarized tunneling of current carriers.     

Thermomechanical model of nonlocal deformation of a solid

We use relations of rational thermodynamics of irreversible processes for a continuous medium with intrinsic state parameters and Eringen’s model of nonlocal theory of elasticity to study the approach to the construction of mathematical models of thermomechanical processes in a deformable body with regard to the effects of temporal and spatial nonlocality of the continuous medium.     

Monoclinic honeycomb-layered compound Li3Ni2SbO6: preparation, crystal structure and magnetic properties

Two synthetic routes-ion-exchange preparation from layered Na(3)Ni(2)SbO(6) at 300 °C and direct solid-state synthesis at 1150 °C resulted in layered Li(3)Ni(2)SbO(6), a cation-ordered derivative from the rocksalt type. The Fddd form reported earlier could not be reproduced. According to the XRD Rietveld analysis, Li(3)Ni(2)SbO(6) is a pseudohexagonal monoclinic structure, C2/m, with a = 5.1828(2) ?, b = 8.9677(3) ?, c = 5.1577(2) ?, β = 109.696(2)°. No Li/Ni mixed occupancy was detected. At high temperatures, the magnetic susceptibility follows the Curie-Weiss law with a positive value of Weiss temperature, ～8 K, indicating a predominance of ferromagnetic interactions. However, Li(3)Ni(2)SbO(6) orders antiferromagnetically at T(N)～ 15 K. The effective magnetic moment is 4.3 μ(B)/f.u. which satisfactorily agrees with theoretical estimations assuming high-spin configuration of Ni(2+) (S = 1). Electron spin resonance (ESR) spectra show single Lorentzian shape line attributed to Ni(2+) ion in octahedral coordination. The absorption is characterized by isotropic temperature independent effective g-factor g = 2.150 ± 0.005. In accordance with the layered honeycomb crystal structure determined for Li(3)Ni(2)SbO(6), the superexchange interaction between Ni(2+) ions through Ni-O-Ni pathways within Ni(2)SbO(6) layers are assumed to be ferromagnetic, while the dominant interaction between layers is antiferromagnetic.     

THE EFFECT OF ACIDS ON THE INFRARED SPECTRA OF SCHIFF BASES—II. IMINES CONTAINING THE C=C-C=N AND C=C-C=C-C=N UNITS

Abstract— The Fourier-transform infrared spectra of chloroform-d solutions of conjugated imines CH₃CH=CHCH=NCH(CH₃)₂ and CH₃CH₂CH=CHCH=CHCH=NCH(CH₃)₂ and the related protonated species with HCl, HBr, HI, trichloro, dichloro, monobromo and monochloroacetic acids or propionic acid are presented. The effects of conjugation and protonation are examined. The results show that conjugation slightly increases the basicity of the Schiff bases. HCl, HBr and HI protonate the Schiff bases completely. The carboxylic acids protonate partially depending on their p K _a, values. When the Schiff base contains two (or more) C=C bonds conjugated with C=N, the main C=C stretching band undergoes a strong intensification showing that sizeable dipole moment variations occur along the conjugated chain.     

Synthesis and crystal and molecular structure of the [Co(HL)Cl<Subscript>2</Subscript>] complex (H<Subscript>2</Subscript>L is an optically active terpene bis-pinane propylenediaminodioxime)

Interaction of Co(II) chloride with optically active bis-pinane propylenediaminodioxime (H₂L) gave a diamagnetic compound of Co(III) with a composition [Co(HL)Cl₂]. The crystal and molecular structure of the compound was determined by X-ray diffraction (XRD) analysis (Enraf-Nonius CAD-4 diffractometer, λMoK_α, 703 F _hkl , R = 0.0347). The crystals are orthorhombic with unit cell parameters a = 8.989(1) Å, b = 12.351(2) Å, c = 22.425(3) Å, V = 2487.7(6) ų, Z = 4, ρ_calc = 1.420 g/cm³, space group P2₁2₁2₁. The crystal structure of the complex is composed of discrete one-center molecules. In the complex, the Co³⁺ ion coordinates four N atoms of the tetradentate cycle-forming ligand (HL^? anion) and two Cl atoms. The coordination polyhedron of Co is a distorted octahedron Cl₂N₄.     

Using solid-phase microextraction combined with gas chromatography-mass spectrometry for the study of the volatile products of biosynthesis released by plants and microorganisms

Published data on the methods and results of study of profiles of volatile biologically active compounds are summarized and discussed. The leading role of gas chromatography-mass spectrometry combined with headspace solid-phase microextraction as an optimum analytical method for determining the qualitative and quantitative composition of volatile organic compounds in in vivo experiments is substantiated. The results of investigation of volatile organic compounds produced by micromycetes of the genus Fusarium are reviewed.     

Crystal structure of bis(semicarbazido)copper(II) nitrate [Cu(NH<Subscript>2</Subscript>NHC(O)NH<Subscript>2</Subscript>)<Subscript>2</Subscript>](NO<Subscript>3</Subscript>)<Subscript>2</Subscript>

The crystal structure of bis(semicarbazido)copper(II) nitrate [Cu(NH₂NHC(O)NH₂)₂](NO₃)₂ has been studied by X-ray diffraction. Monoclinic crystals, a = 6.835(2) Å, b = 7.733(2) Å, c = 10.320(3) Å, β = 105.701(3)°, V = 525.1(2) ų, space group P2₁/c, Z = 2, d _msd = 2.136 g/cm³, μ(MoK _α) = 2.143 mm⁻¹. The structure was solved with the program for automatic analysis of Patterson’s function and refined by full-matrix least squares in an anisotropic approximation for all non-hydrogen atoms using 753 independent reflections; R ₁ = 0.0203. The square environment of the Cu atom is formed from the amino nitrogen atoms of the hydrazine fragments and the C=O oxygen atoms of the two semicarbazide bidentate molecules (Cu-N 1.928 Å, Cu-O 1.999 Å). The axial positions are occupied by the O atoms of the NO ₃ ⁻ outer-spheric anions (Cu-O 2.505 Å). In the structure, the complex cations and the NO ₃ ⁻ anions are linked into a framework by N-H...O type hydrogen bonds. Original Russian Text Copyright ? 2007 by G. V. Romanenko, Z. A. Savelieva, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 2, pp. 370–373, March–April, 2007.     

High resolution diffraction and small angle scattering neutron investigations of LaCo<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>O<Subscript>3+</Subscript><Subscript>δ</Subscript>: effect of oxygen content

We have investigated LaCo_0.5Mn_0.5O_{3+ δ} compounds with different oxygen content by means of magnetization, high resolution and small-angle neutron diffraction measurements. Oxygen content decrease down to stoichiometric composition leads to an essential increase of T_C and magnetic moment while Co/Mn ionic ordering degree is kept almost constant. It is assumed that upon oxygen reduction Co³⁺ ions change their valence state down to 2+ one that leads to dominating of Co²⁺-Mn⁴⁺ ferromagnetic interactions as well as T_C increase. Magnetic properties can be explained in terms of coexistence of long-range ferromagnetic order and short-range clusters with antiferromagnetic interactions prevailing. Size distribution of the mentioned short-range magnetic inhomogeneities is rather mild within the samples but it is strongly temperature dependent.     

Structure of the Cu(II) chloride complex with 4-amino-l,2,4-triazole Cu(C2H4N4)Cl2

The coordination compounds of copper(II) chloride and bromide with 1,2,4-triazole (L¹) and 4-amino1,2,4-triazole (L²), CuL¹Hal₂ and CuL²Hal₂, possess interesting magnetic properties [1, 2]. For example, at very low temperatures CuL¹Cl₂ and CuL¹Br₂ are ferromagnets [2](T _c ≈ 3.3 and 6.5 K, respectively). To explain the magnetic behavior of copper(II) halide complexes with the above nitrogen heterocycles it is generally assumed that the complexes are polynuclear chain compounds in which the copper atoms are bridged by two halogen ions and bridging bidentate heterocycle molecules (coordination of N1 and N2 atoms). This hypothesis is made on the basis of the X-ray diffraction analysis of CuL¹Cl₂ [3]. It is interesting to perform an X-ray diffraction study of CuL²Cl₂ and CuL2Br2; this is important for obtaining reliable magnetostructural correlations for this group of compounds. In this study, we investigated single crystals of the complexes; this demanded choosing special conditions of synthesis, which differ from the conditions suggested for the synthesis of polycrystals in [1]. In this communication we report on the results of synthesis and X-ray diffraction analysis of the single crystals of the coordination compound CuL²Cl₂. Translated fromZhurnal Strukturnoi Khimii, Vol. 38, No. 1, pp. 207–212, January–February, 1997.