ESR study of some solvent effects of the Cu(II)-aspirinate complex

Powder ESR spectra of the [Cu₂(Asp)₄](H₂O)₂ complex show the existence of Cu(II) acetate like dimers characterized by a strong antiferromagnetic exchange interaction (J=?288 cm^?1). In pyridine-dimethylformamide solutions the monomeric species prevail. Two different monomeric species, the Cu(DMF)₄ of planar-distorted tetrahedral (T_d) symmetry and the Cu(Asp)₂(DMF)₂ with elongated tetrahedral-octahedral symmetry were evidenced in DMF solution adsorbed on NaY zeolite. In 40 % Py+60 % DMF solution two monomeric species were also identified. These are Cu(Asp)₂(DMF)₂ and Cu(Asp)₂(Py)₂, the last species having a CuN₂O₂ chromophore in atrans squareplanar arrangement. In pyridine Cu(II)-aspirinate solution only the Cu(Py)₄ monomeric species of CuN₄ chromophore was evidenced.     

ESR study of some Cu(II)-4-substituted-2-Thiazolylhydrazone complexes

The Cu(II) complexes with 2-N-acetyl-salicylidene-hydrazino-4-chlor-methyl thiazole (L.) and 2-N-acetyl salicylidene-hydrazioo-4-thiazolyl acetic ester (L_II) were prepared and investigated by ESR measurements. The powder ESR spectrum at room temperature of CuL_IICl is quasi-isotropic (g=2.113), while for CuL_IICl is characteristic of monomeric species with axial symmetry (g _II)=2.234,g ₁=2.073). The isotropic ESR spectra of the CuLCl compounds in DMSO solution suggest the presence of pseudo-tetrahedral monomeric species. The anisotropic spectra were obtained for adsorbed CuLCl DMSO solutions on NaY zeolite. The parallel hyperfine structure shows the coexistence of two magnetic nonequivalent monomeric species. The estimation of some LCAO-MO coefficients using Kivelson and Neiman’s approximation reveals a dominant ionic character for copper-ligand bonds.     

ESR study of Cu(II)-indomethacin and its pyridine and DMF adducts

Powder ESR spectra of [Cu₂(Ind)₄](H₂O)₂ at room temperature show the presence of copper acetate like dimers characterized by a strong antiferromagnetic exchange interaction (J≈?338 cm^?1). Two different monomeric species were evidenced in 40%Py+60%DMF solution absorbed on NaY zeolite: the Cu(Ind)₂(DMF)₂ with an elongated tetragonal-octahedral symmetry and the Cu(Ind)₂(Py)₂ with a CuN₂O₂ chromophore in atrans square-planar arrangement. Only one monomeric species Cu(Ind)₂(Py)₂ was identified in 20%Py+80%DMF and 20%Py+80% Chloroform solutions. The Cu(Py)₄ ²⁺ species of CuN₄ chromophore occurs in pyridine Cu(II)-indomethacin solution suggesting a decomposition of the solvit compound.     

Study of ethylene adsorption on zeolite NaY modified with group I metal ions

The adsorption of ethylene by zeolite NaY and zeolite NaY modified by cation exchange with potassium, rubidium, and cesium ions was studied. Cation exchanges were carried out using KNO₃, RbNO₃, and CsNO₃ in the concentration ranges of 0.2-10 mM. XRD patterns and specific surface areas illustrated that modification of NaY zeolite by very dilute solutions containing K⁺, Rb⁺ and Cs⁺ did not lead to significant changes in the crystallinity. Analysis of metals content (ICP-OES) showed that Cs⁺ can replace Na⁺ better than Rb⁺ and K⁺. Particle analysis indicated slight decreases in surface area but pore volumes and pore diameters remained unchanged. Ethylene adsorption isotherms indicated that Na-Y zeolite which was modified by 5.0 mM KNO₃, 0.5 mM RbNO₃ and 1.0 mM CsNO₃ could adsorb ethylene better than zeolite Na-Y. K-NaY zeolite adsorbed up to 102.45 cm³/g ethylene, while Rb-NaY and Cs-NaY zeolites adsorbed up to 98.50 cm³/g and 90.15 cm³/g ethylene, respectively. Ethylene adsorption capacities depended on number of adsorption sites and surface interactions.     

EPR Studies of CuCl2-ethanolate Complexes

The molecular and electronic structure of the CuCl₂-complexes with monoethanolamine (MEA) and triethanolamine (TEA), and their dynamical properties in solid and in DMF solutions were discussed on the basis of EPR measurements. Measurements indicate a dimeric structure of CuCl₂-MEA complexes with very weak Cu-Cu coupling. Intradimer superexchange interaction is temperature dependent and decreases with temperature. In CuCl₂-TEA monomeric complexes exist with a significant vibronic effect which is due to a change of d_Z2 admixture to the d x²-y² ground state when temperature is changed.     

Zero-field splitting and local structure for V<Superscript>2+</Superscript> ions in CsMg<Emphasis Type="Italic">X</Emphasis><Subscript>3</Subscript> (<Emphasis Type="Italic">X</Emphasis>=Cl,Br, I) crystals

The zero-field splitting and local structure for V²⁺ ions in CsMgX ₃ (X =Cl, Br, I) crystals are theoretically investigated using complete diagonalization method (CDM) for a 3d ³ ion in trigonal symmetry. Spin-spin (SS) and spin-other-orbit (SOO) interactions are taken into account in addition to the general spin-orbit (SO) interaction. On this basis, using ligand ion displacement model, we find that the ligand ions move away from C ₃-axis, and therefore the local angles in the V²⁺ centres are larger than the angles in the hosts. The results show good agreement with the observed values.     

Theoretical studies on dielectronic recombination of neonlike gold and its effects on plasma ionization balance and radiation energy

The dielectronic recombination (DR) of neonlike gold ions is investigated employing the flexible atomic code based on the relativistic configuration interaction method, and its influence on the ionization balance and radiation energy in high-temperature plasma is also studied. The total resonance strength for LMM configuration complex is in a good agreement with the experimental measurement and other theoretical works. The DR rate coefficients are calculated and compared with the three-body recombination and radiative recombination rate coefficients. The DR process is the dominant recombination mechanism of Ne-like gold ions for plasma with temperature T_e≥6.5 keV and density n_e≤2×10²² cm^-3, which is close to the condition of X-ray conversion region in the inertial confinement fusion. Moreover, the DR satellite spectra of LMM, LMN and LMO resonances are simulated, and compared with the intensities of the corresponding resonance lines induced by the electron impact excitation. The intensity ratio of the satellite line 3D’ [(2p⁵_3/23d_3/23d_5/2)_J=5/2[(2p^{5}_{3/2}3d_{3/2}3d_{5/2})_{J=5/2}–(2p⁶3d_3/2) _J=3/2](2p^{6}3d_{3/2})_{ J=3/2}] and the resonance line 3D [(2p⁵_3/23d_5/2)_J=1[(2p^{5}_{3/2}3d_{5/2})_{J=1}–(2p⁶)_J=0](2p^{6})_{J=0}] is given, which can be applied for diagnostics of plasma temperature.     

Combined XPS,electrochemical and Kelvin probe measurements of NaY zeolite

In the present study X-ray Photoelectron Spectroscopy (XPS) combined with in situ electrochemical and Kelvin probe measurements was used in order to get a deeper insight on the mechanism of the cation transport through NaY zeolite and the charge transfer through the Au electrode/zeolite interface. It is shown that by imposing a potential gradient across the NaY powder which is sandwiched between two electrodes, Na⁺ ions can be electrically transferred to or from the Au working electrode area, following the direction of the applied potential between the two electrodes. Two peaks corresponding to sodium species were detected by means of in situ XPS investigation during potential application. The first peak of Na1s photoelectrons with binding energy at 1072.2 ± 0.2 eV is attributed to Na adsorbed on the grounded Au electrode with its coverage remaining unchanged upon potential imposition. The second peak is directly associated with Na present in the zeolite and upon potential application its binding energy varies proportionally with the variation of the surface potential measured by Kelvin probe. Upon varying the potential from − 4 to + 4 V between the working and counter electrode, the Na⁺ concentration decreases by ca30% at the Au/zeolite interface. However the invariant amount of Na on the Au electrode under vacuum shows that the variation in Na⁺ concentration is not due to ionic transfer onto the Au surface but instead Na⁺ accumulation can be assumed at the Au/zeolite interface. On the other hand, current or potential application under O₂ atmosphere promotes the electrocatalytic reaction of Na⁺ towards the formation of Na₂O on the Au electrode surface.     

Color centers in the ionized and in the triplet state —Z 2 centers in ytterbium-doped KCl crystals

Z ₂ centers in Yb²⁺-doped KCl crystals are investigated by optical absorption experiments and by ESR experiments using the optically excited triplet state. Two mainZ ₂ center configurations have been found. One of them shows (100) axial symmetry and is optically orientable in the crystal. The other one possesses (110) symmetry elements. The measured fine structure constants are explained partly by dipole-dipole interaction of the two electronic magnetic moments partly by spin orbit interaction due to the Ytterbium impurity. The structure of the optical absorption spectra is attributed to as ²–s d charge transfer transition affected by the combined effect of crystal field and spin orbit interaction.     

Identification of Structure and Position of Cu(II) Ion in Aquomethylmelonatozinc(II) Host by Powder XRD, EPR, FT-IR and UV–Vis Spectroscopy

Single-crystal electron paramagnetic resonance studies of Cu(II)-doped aquomethylmelonatozinc(II) are carried out at 300 K. Angular variation of copper hyperfine lines in the three orthogonal planes shows the presence of a single site in substitutional position, with spin Hamiltonian parameters: g ₁₁ = 2.076, g ₂₂ = 2.100, g ₃₃ = 2.379; A ₁₁ = 2.40 mT, A ₂₂ = 3.22 mT and A ₃₃ = 13.47 mT. The low value for the hyperfine structure parameter value for A ₃₃ has been explained by taking into account a considerable admixture between d_{x² - y²} d_{{x^{2} - y^{2} }} ground state and d_z² d_{{z^{2} }} excited state, with admixture coefficients being a = 0.291, b = 0.951, c = 0.054, d = 0.031 and e = −0.031, where coefficients a and b correspond to coefficients for d_z² d_{{z^{2} }} and d_{x² - y²} , d_{{x^{2} - y^{2} }} , respectively. Few other calculated parameters such as κ = 0.35, P = 303 × 10⁻⁴ cm⁻¹; α = 0.88 and α′ = 0.47 indicate considerable covalency. Powder X-ray diffraction, Fourier transform infrared and ultraviolet-visible data confirm the structure of host complex and presence of the dopant.     

Microstructured hydroxyl environments and Raman spectroscopy in selected basic transition-metal halides

Raman vibrational spectra of the selected basic (hydroxyl OH and deuteroxyl OD) transition-metal halides, geometrically frustrated material series α-, β-, γ-Cu₂(OH)₃Cl, α-Cu₂(OH)₃Br, β-Ni₂(OH)₃Cl, β-Co₂(OH)₃Cl, β-Co₂(OH)₃Br, γ-Cu₂(OD)₃Cl, and β-Co₂(OD)₃Cl are measured at room temperature and analysed to investigate the relationship between the microstructured OH environments and their respective Raman spectra. Among these selected samples, the last two are used to determine the OH stretching vibration region (3600 cm^-1—3300 cm^-1) and OH bending vibration region (1000 cm^-1—600 cm^-1) of OH systems in the spectra. Through the comparative analysis of the distances d(metal—O), d(O—halogen), and d(OH), the strong metal—O interaction and trimeric hydrogen bond (C_3v, C_s or C₁ symmetry) are found in every material, but both determine simultaneously an ultimate d(OH), and therefore an OH stretching vibration frequency. According to the approximately linear relationship between the OH stretching vibration frequency and d(OH), some unavailable d(OH) are guessed and some doubtful d(OH) are suggested to be corrected. In addition, it is demonstrated in brief that the OH bending vibration frequency is also of importance to check the more detailed crystal microstructure relating to the OH group.     

ESR study of the ferrimagnetic spinel selenide CuCr2Se4

Ferrimagnetic spinel selenide CuCr₂Se₄ has been investigated by the electron spin resonance (ESR) spectroscopy. Experimental results reveal that ESR signals originate from the localized d-shell electrons of Cr³⁺ ions. In addition, the ESR linewidth ΔH _PP increases linearly with decreasing temperature. It is suggested that the spin-orbit coupling may be one of the contributions to the broadening of ΔH _PP . Our ESR results support the model of the ferrimagnetic hybridization between localized 3d ³ electrons of Cr³⁺ with delocalized holes of Se 4p band.     

Reaktion von Pyridin-2-Carbonsäure Mit Tetrabutylammonium-Tetrachloro-Nitridotechnetat(VI) Sowie Tetrabutylammonium-Tetrachlorooxotechnetat (V)

Abstract

The reaction of 2-pyridine carboxylic acid (Hpic) with (n-Bu₄N)[TcNCl₄] and (n-Bu₄N)[TcOCl₄] in ethanol and methanol, respectively, yields the dinuclear μ-oxo complex [(pic)₂NTc-O-TcN(pic)(Hpic)Cl] and the monomeric complex [TcO(pic)₂Cl].

Visible and infrared spectroscopy, ESR, ¹H-NMR and ⁹⁹Tc-NMR have been used to characterize the new compounds. The most important field of application for the new compounds synthesized is radiodiagnostics.     

ESR of selenium pairs (Se+2) in silicon

A slight anisotropy of the Se⁺₂ ESR is resolved, revealing [111] axial symmetry. The pair groundstate is a_2u in D_3d symmetry, consistent with the almost complete s-character at the Se sites. The value of g₆ is correlated with the binding energy of Se⁺₂ in a way recently established for simple deep donors in Si.     

High sensitivity GMR with small hysteresis in Ni–Fe/Cu multilayers

Giant magnetoresistance (GMR) effect and magnetisation reversal processes have been investigated in Py/Cu(Py=Ni₈₃Fe₁₇,permalloy) multilayers (Mls) obtained by face-to-face sputtering method. The investigated films had constant sublayer thicknesses both for Py and Cu (d_Cu=2nm,d_Py=2nm) and various numbers of ferromagnetic sublayers. It has been shown that for such Mls a high field sensitivity of GMR effect (S≈0.4%/Oe) and negligible hysteresis can be obtained for a low number of Py layers.     

Electron spin resonance and optical spectroscopic studies of Co-ZSM-5 with nitric oxide

The reaction of nitric oxide with ZSM-5 zeolite ion-exchanged by Co(II) (Co-ZSM-5) has been studied by electron spin resonance (ESR), Fourier transform infrared (FTIR) and diffuse reflectance ultraviolet-visible spectroscopy. When dehydrated Co-ZSM-5 reacts at room temperature with nitric oxide, the ESR spectrum of Co(II) atg = 5.5, which is only observable below 45 K, is greatly reduced and a new⁵⁹Co hyperfine octet forms at g_avg = 2.11. The overall Co(II) ESR intensity decreases by about 50% which suggests formation of some diamagnetic cobalt complex. Mononitrosyl cobalt complexes such as Co(I)-NO⁺ or less probably Co(III)-(NO)⁻ are suggested as possible precursors of a dintrosyl cobalt complex. The octet indicates hyperfine interaction with⁵⁹Co and is associated with a cobalt dinitrosyl complex. FTIR bands at 1813 and 1896 cm⁻¹ confirm a dinitrosyl species and a broad band from 1600–1800 cm⁻¹ is tentatively interpreted as a mononitrosyl species. The visible spectrum for dehydrated Co-ZSM-5 shows a tetrahedral Co(II) band from 500–700 nm with three components which disappears after NO adsorption at room temperature. We suggest that Co(0)-(NO)₂²⁺ forms after NO adsorption onto Co(II)-ZSM-5 zeolite on the basis of ESR and ultraviolet-visible spectroscopy.     

Anomalous concentration dependence of the coordination behavior of Cl− ion to Ln3+ ion (Ln3+ = rare‐earth ion) in anhydrous LnCl3 alcohol solutions

Raman spectroscopic measurements were carried out for the anhydrous LnCl₃·20ROH·XLiCl solutions (Ln³⁺ = La³⁺− Lu³⁺, X = 0–3; ROH = MeOH, EtOH, n‐PrOH) in the liquid state. The salt concentration (X) dependence of the wavenumber for the Ln–Cl stretching Raman band (ν_Ln–Cl) is examined in conjunction with the formation of chloro‐rare‐earth complexes. We have obtained very intriguing results including the fact that the chloro complexations of the middle rare‐earth ions (e.g. gadolinium, holmium ions, etc.) in the MeOH and EtOH solutions show peculiar behavior with regard to the salt concentration dependence: the ν_Ln–Cl wavenumber increases with the increasing chloride concentration. However, the ν_Ln–Cl wavenumbers of the light and heavy rare‐earth (e.g. lanthanum, lutetium, etc.) salt solutions show normal behavior; i.e. ν_Ln–Cl decreases with the increasing chloride concentration. On the other hand, in the n‐PrOH solutions, the ν_Ln–Cl frequency in the solutions of all the rare‐earth elements exhibits a normal behavior. We now present a possible mechanism for this anomalous concentration dependence of coordination of Cl⁻ ions to Ln³⁺ ions in anhydrous LnCl₃ alcohol solutions. Copyright © 2007 John Wiley & Sons, Ltd.     

An E.S.R. study of electron irradiated K3IrCl6 in a NaCl host lattice

Electron irradiation of the diamagnetic [Ir^IIICl₆]^3- ion in a NaCl host lattice produces two paramagnetic species. ESR studies indicate that these slightly different species can be assigned to a [Ir^IICl₆]^4- complex, with 5d ⁷ low spin configuration, arising from the capture of an electron in a d_z ² orbital. The almost zero value for the quadrupolar interaction and the negative value for the core polarization field per unpaired spin are discussed in terms of a ligand field theory and the group overlap integral for the A _1g molecular orbital is calculated from the experimental data.     

ESR investigation of some copper(II)-dioxime-dichloride compounds

The following copper(II)-dioxime-dichloride compounds: [Cu(G)Cl₂]₂, [Cu(P)Cl₂]₂, [Cu(DMG)Cl₂]₂ and [Cu(O)Cl₂]₂ (where G=C₂H₄O₂N₂, P=C₃H₆O₂N₂, DMG=C₄H₈O₂N₂, O=C₈H₁₄O₂N₂) were investigated by ESR method. Spectra of powder samples obtained in the g?2 region suggest the presence of triplet ground state (S=1) realized by a weak ferromagnetic exchange coupling. In liquid and frozen solutions the monomeric species (S=1/2) prevail. Some delicate changes in the coordination polyhedra symmetry in terms of ligand molecules and solvents nature were evidence. A 4p-admixture degree of 2% in the d_xy ground state was estimated for pseudotetrahedral (Td) species in frozen solutions.     

Adsorption of NO and N2O on Fe-BEA and H-BEA zeolites

FT-IR (Fourier-transform infrared) spectroscopy and density function theory (DFT) methods have been applied to the investigation of the interaction of NO and N₂O with Fe³⁺ species in a beta zeolite (BEA). The geometries for H-BEA and Fe-BEA represented as 10T cluster, and NO and N₂O adsorption on them in η¹-O and η¹-N modes have been completely optimized. The results show that NOx could be adsorbed on Fe³⁺ species and Brønsted acid sites in two modes, but NOx is mainly bonded by N to H or Fe atom and the iron site is preferred. NOx adsorbed on Fe³⁺ species is more stable than on Brønsted acid sites. Adsorption energies for N₂O and NO follow the order of NO > N₂O, predicating that the affinity of NO molecule on BEA zeolite is much stronger than N₂O molecule on BEA zeolite.