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51.
N. V. Chernei V. A. Nadolinnyi N. V. Ivannikova V. A. Gusev I. N. Kupriyanov V. N. Shlegel Ya. V. Vasiliev 《Journal of Structural Chemistry》2005,46(3):431-437
Comprehensive investigations have been performed by EPR and optical spectroscopy for Bi3GeO4 crystals doped with chromium ions. It is demonstrated that the known optical absorption spectrum for chromium ions, specifically,
the triplet in the region 600–900 nm has an analog in the EPR spectra — the center with electron spin S = 1. The spectrum is described by the spin-Hamiltonian with the parameters D = 550 G, E = 10 G, g
xx
= g
yy
= 1.915, g
zz
= 1.932. The EPR spectrum is dictated by Cr4+ incorporation at the germanium sites. Luminescence observed in the region 1.2–1.7 μm is also caused by transitions of Cr4+ with tetrahedral surroundings to germanium sites.
Original Russian Text Copyright ? 2005 N. V. Chernei, V. A. Nadolinnyi, N. V. Ivannikova, V. A. Gusev, I. N. Kupriyanov, V.
N. Shlegel, and Ya. V. Vasiliev
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 3, pp. 444–450, May–June, 2005. 相似文献
52.
Mario Chiesa Maria Cristina Paganini Elio Giamello Cristiana Di Valentin Gianfranco Pacchioni 《Chemphyschem》2006,7(3):728-734
(H+)(e-) pairs generated at the surface of polycrystalline CaO are analyzed for the first time in terms of the interaction of the unpaired electron spin with the nuclear spin of the 17O anions of the surface. CaO crystals enriched in the 17O isotope are prepared and the corresponding hyperfine coupling constants are measured in electron paramagentic resonance (EPR) spectra. The results are analyzed on the basis of cluster model density functional theory calculations. The computed hyperfine coupling constants for (H+)(e-) pairs formed on the edge, corner, and reverse corner sites of the CaO surface allow a tentative assignment of two observed spectral features to specific morphological surface sites. 相似文献
53.
Maurí cio Braga de Araú jo Nelson Moreira Pinhal Ney Vernon Vugman 《Radiation Physics and Chemistry》2002,64(5-6):389-393
The kinetics of oxidized and reduced Ni2+ complexes produced by X-ray irradiation on single crystals of NaCl doped with [Ni(CN)4]2− is studied by Electron Paramagnetic Resonance at room temperature. The interdependent generation of these two complexes is attributed to migration of the charge compensating vacancy from the reduced to the oxidized complex in a reversible reaction. At higher X-ray doses, there is a predominant formation of the reduced complex. 相似文献
54.
Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme. 相似文献
55.
A.M. Wasserman V.A. Kasaikin V.P. Timofeev 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1998,54(14):2295-2308
The rotational mobility of spin probes of different shape and size in low molecular and polymer micelles has been studied. Several probes having nitroxide fragment localized either in the vicinity of micelle interface or in the hydrocarbon core have been used. Upon increasing the number of carbon atoms in hydrocarbon chain of detergent from 7 to 13 (sodium alkyl sulfate micelles) or from 12 to 16 (alkyltrimethylammonium bromide micelles) the rotational mobility of spin probes is decreased by the factor 1.5–2.0. The spin probe rotational mobility in polymer micelles (the complexes of alkyltrimethylammonium bromides and polymethacrylic or polyacrylic acids) is less than mobility in free micelles of the same surfactants. The study of EPR-spectra of spin labeled polymethacrylic acid (PMA) indicated that formation of water soluble complexes of polymer and alkyltrimethylammonium bromides in alkaline solutions (pH 9) does not affect the polymer segmental mobility. On the other hand, the polymer complexes formation in slightly acidic water solution (pH 6) breaks down the compact PMA conformation, thus increasing the polymer segmental mobility. Possible structures of polymer micelles are discussed. 相似文献
56.
Detailed EPR and ENDOR experiments on the cocrystalline complex of 1-methyluracil:9-Ethyladenine (MUEA) have revealed that the major radiation-induced products observed at 10 K on MU are: MUEA1, a radical formed by net hydrogen abstraction from the N1-CH3 methyl group, MUEA2, the MU radical anion, and MUEA3, the C5 H-addition radical. The following four products were observed on the adenine moiety at 10 K, MUEA4, the N3 protonated adenine anion, MUEA5, the native adenine cation, MUEA6, the amino deprotonated adenine cation, and MUEA7, the C8 H-addition radical formed by net H-addition to C8 of the adenine base. The geometries, energetics, and hyperfine properties of all possible radicals of MU and EA, the native anions and cations, as well as radicals formed via net hydrogen atom abstraction (deprotonated cations) or addition (protonated anions) were investigated theoretically. All systems were optimized using the hybrid Hartree–Fock–density functional theory functional B3LYP, in conjunction with the 6-31G(d,p) basis set of Pople and co-workers. Calculations of the anisotropic hyperfine couplings for all the radicals observed in MUEA are presented and are shown to compare favorably with the experimentally measured hyperfine couplings. The calculated ionizations potentials indicate that EA would be the preferred oxidation site. In MUEA, both the adenine cation and its N4-deprotonated derivative were observed. The calculated electron affinities indicate that MU would be the preferred reduction site. In MUEA radical, MUEA2 is a uracil reduction product, however the protonation state of this radical could not be determined experimentally. Calculations suggest that MUEA2 is actually the C4=O protonated anion. 相似文献
57.
Tapan Kumar Lal John F. Richardson Mark S. Mashuta Robert M. Buchanan Rabindranath Mukherjee 《Polyhedron》1997,16(24):1248-4336
Synthesis and characterization of a nitrite-bound copper(II) compound [CuL4)2(ONO)]ClO4 have been achieved (L4 = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L4 provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Å. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the dx2−y2 orbital. Variable-temperature (80–300 K) magnetic susceptibility measurements in the solid state as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible CuII---CuI response [cathodic peak potential, Epc (V vs saturated calomel electrode (SCE)): −0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to reversible CuII---CuI redox response [
]. 相似文献
58.
59.
EPR, UV/Vis and FTIR spectroscopy as well as thermal analysis (TA/MS) were applied to study the influence of sulfate species present in the anatase support on the specific nature of VOx species in supported VOx/TiO2 catalysts. Those sulfate species modify the local structure of the supported vanadyl species and lead to the formation of two types of VO2+ sites instead of only one type being formed on sulfate‐free anatase. EPR and FTIR spectroscopic measurements revealed that a part of the VO2+ species are directly bound to the surface sulfate species. By TA/MS it was found that SO2 is released at lower temperature from VOx/TiO2 in comparison to the vanadium‐free support. The direct bonding between sulfate and VOx species stabilizes the latter on the surface of VOx/TiO2 resulting in three effects: 1) a higher V site dispersion in comparison to sulfate‐free TiO2, 2) a better resistance of surface vanadyls against diffusion into the bulk of the support and 3) a much faster reoxidation of reduced V sites than observed on sulfate‐free TiO2. 相似文献
60.