Mössbauer Spectra (mössbauer + spectrum)

Distribution by Scientific Domains

Selected Abstracts

Unconventional Spin Crossover in Dinuclear and Trinuclear Iron(III) Complexes with Cyanido and Metallacyanido Bridges

Abstract A nonsymmetrical triamine, 1,6-diamino-4-azahexane, was Schiff-condensed with (X-substituted) o -salicylaldehyde to yield pentadentate ligands X-L5: salpet and MeBu-salpet. These ligands form mononuclear, dinuclear, and trinuclear FeIII complexes, whose structures were determined by single-crystal X-ray analysis. Of the mononuclear complexes, [FeIII(salpet)Cl] and [FeIII(MeBu-salpet)Cl] are high spin (S = 5/2), whereas [FeIII(salpet)CN]·MeOH is low spin (S = 1/2). The dinuclear and trinuclear complexes show a kind ofthermally induced spin crossover. The dinuclear complex [L5FeIII(CN)FeIIIL5](ClO4)·2H2O (L5 = salpet) is a mixed-spin assembly: the C -coordinated FeIII center is low spin (L) and the N -coordinated FeIII center is high spin (H) at low temperature; an antiferromagnetic interaction occurs between them. This LH reference state is mixed with the LL one. Upon heating, the system shows an increasing content of the HH state. Also, the dinuclear complex [L5FeIII(CN)FeIIIL5](BPh4)·2MeCN (L5 = MeBu-salpet) exhibits a spin transition between LH and HH spin pairs. The mixed-valence trinuclear complex [L5FeIII{FeII(CN)5(NO)}FeIIIL5]·0.5MeOH·3.75H2O (L5 = salpet) shows spin crossover with a residual high-spin fraction at liquid He temperature owing to the LL + LH ground state. The metallacyanido-bridged complex [L5FeIII{Ni(CN)4}FeIIIL5]·2MeOH (L5 = MeBu-salpet) contains a high-spin pair, HH, over the whole temperature interval with a ferromagnetic exchange interaction. A theoretical model was outlined that allows simultaneous fitting of all available experimental data (magnetic susceptibility, magnetization, high-spin mole fraction obtained from the Mössbauer spectra) on a common set of parameters. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Valence-Tautomeric RbMnFe Prussian Blue Analogues: Composition and Time Stability Investigation

Lionel Salmon
Abstract Three different stoichiometric forms of RbxMn[Fe(CN)6]y·zH2O [x = 0.96, y = 0.98, z = 0.75 (1); x = 0.94, y = 0.88, z = 2.17 (2); x = 0.61, y = 0.86, z = 2.71 (3)] Prussian blue analogues were synthesized and investigated by magnetic, calorimetric, Raman spectroscopic, X-ray diffraction, and 57Fe Mössbauer spectroscopic methods. Compounds 1 and 2 show a hysteresis loop between the high-temperature (HT) FeIII(S = 1/2),CN,MnII(S = 5/2) and the low-temperature (LT) FeII(S = 0),CN,MnIII(S = 2) forms of 61 and 135 K width centered at 273 and 215 K, respectively, whereas the third compound remains in the HT phase down to 5 K. The splitting of the quadrupolar doublets in the 57Fe Mössbauer spectra reveal the electron-transfer-active centers. Refinement of the X-ray powder diffraction profiles shows that electron-transfer-active materials have the majority of the Rb ions on only one of the two possible interstitial sites, whereas nonelectron-transfer-active materials have the Rb ions equally distributed. Moreover, the stability of the compounds with time and following heat treatment is also discussed.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Mössbauer Investigation of Peroxo Species in the Iron(III),EDTA,H2O2 System

Virender K. Sharma
Abstract The reaction of a diiron(III),EDTA complex with H2O2 in alkaline medium is studied by Mössbauer spectroscopy in conjunction with the rapid-freeze/quench technique in order to identify possible intermediate species during the formation and decomposition of the purple (EDTA)FeIII(,2 -O2)3, complex ion. Starting from the six-coordinate [FeIIIEDTA], species at acidic pH, it is demonstrated that mononuclear complexes formed at a pH of about 1 are convert into the diiron(III),EDTA complex [(EDTA)FeIII -O-FeIII(EDTA)]4, upon raising the pH to around 10.4. H2O2 reacts with the diiron(III) complex to give peroxide/hydroperoxide related adducts. Initially, the reaction tears apart the dimers to form a peroxo adduct, namely the seven-coordinate mononuclear [(EDTA)FeIII(,2 -O2)]3,, which is stable only at very high pH. The decomposition of this peroxo adduct gives two new species, which are reported for the first time. The Mössbauer parameters of these species suggest a six-coordinate ,-peroxodiiron(III) complex [(EDTA)FeIII -(OO)-FeIII(EDTA)]4, and a seven-coordinate ,-hydroxo-,-peroxodiiron(III) complex [(EDTA)FeIII -(OO)(OH)-FeIII(EDTA)]5,. A badly resolved, extremely broad component is observed in the Mössbauer spectra during the conversion of the monomer to dimeric peroxo species, which may be attributed to the short-lived [(EDTA)FeIII -OO]3, or [(EDTA)FeIII -OOH]2, intermediate species. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Anomalous Spin Transition Observed in Bis(2,6-bis(pyrazol-3-yl)pyridine)iron(II) Thiocyanate Dihydrate,

A. Bhattacharjee
Abstract Bis(2,6-bis(pyrazol-3-yl)pyridine)iron(II) thiocyanate dihydrate undergoes a two-step singlet (1A1) , quintet (5T2) transition in which both steps are associated with thermal hysteresis. Thermal cycling of the sample results in its conversion to a second phase which displays a single-step transition with a very narrow hysteresis loop. This second phase slowly reverts to the initial phase on standing at 300 K. The interconversions are completely reversible. The spin state changes have been monitored by measurement of magnetism and Mössbauer spectra and by differential scanning calorimetry (DSC) studies. [source]

Ferric iron in SNC meteorites as determined by Mössbauer spectroscopy: Implications for martian landers and martian oxygen fugacity

M. Darby DYAR
Also, considerable current effort is being made to understand the oxygen fugacity of martian magmas because of the effect of fO2 on mineral chemistry and crystallization processes. For these 2 reasons, the present study was conceived to acquire room temperature Mössbauer spectra of mineral separates and whole rock samples of 10 SNC meteorites. The results suggest that mineral identification using remote application of this technique will be most useful when the phases present have distinctive parameters arising from Fe in very different coordination polyhedra; for example, pyroxene coexisting with olivine can be discriminated easily, but opx versus cpx cannot. The MER goal of using Mössbauer spectroscopy to quantify the relative amounts of individual mineral species present will be difficult to satisfy if silicates are present because the lack of constraints on wt% FeO contents of individual silicate phases present will make modal calculations impossible. The remote Mössbauer spectroscopy will be most advantageous if the rocks analyzed are predominantly oxides with known stoichiometries, though these phases are not present in the SNCs. As for the detection of martian oxygen fugacity, no evidence exists in the SNC samples studied of a relationship between Fe3+ content and fO2 as calculated by independent methods. Possibly, all of the Fe3+ observed in olivine is the result of dehydrogenation rather than oxidation, and this process may also be the source of all the Fe3+ observed in pyroxene. The observed Fe3+ in pyroxene also likely records an equilibrium between pyroxene and melt at such low fO2 that little or no Fe3+ would be expected. [source]

Superparamagnetic iron oxide particles: contrast media for magnetic resonance imaging,

Rüdiger Lawaczeck
Abstract The mainstream magnetic iron oxide particles used as contrast media for magnetic resonance (MR) imaging are composed of a magnetic iron oxide core surrounded by a dextran or carboxydextran coat. The core size ranges from 2 nm to less than 10 nm, and the hydrodynamic diameter ranges from 20 nm to about 120 nm. The coat prevents aggregation and sedimentation of the particles in aqueous solutions, achieves high biological tolerance, and prevents toxic side effects. Two kinds of particles are considered: (i) large particles (>30 nm), called superparamagnetic iron oxide particles (SPIOs) for liver imaging; (ii) smaller particles (<30 nm hydrodynamic diameter), called ultrasmall SPIOs (USPIOs), e.g. for MR angiography. To characterize the particles, Mössbauer spectra are presented for the two particle ensembles. These spectra allow insight into the magnetic coupling, the valency of the iron ions and a rough estimate of the core size to be deduced. On the basis of the concentration dependence of the MR signal intensities, two applications are discussed together with two representative clinical examples. Future indications for MR diagnostics, e.g. the labeling and tracking of stem cells during stem-cell therapy control, are outlined. Copyright © 2004 John Wiley & Sons, Ltd. [source]

Speciation of some triorganotin compounds in sediments from the Anacostia and Potomac Rivers, Washington, DC, using Mössbauer spectroscopy

George Eng
Abstract Triorganotin compounds, namely the tributyltin (TBT) and triphenyltin (TPT) moieties, have been used as the active components in antifoulant marine paints. Mössbauer spectroscopy was used in this work to identify the products of speciation of these triorganotin compounds in various types of sediment from rivers around the Washington, DC, USA, area. Aerobic and anaerobic sediments from several sites in the Anacostia and Potomac Rivers were spiked with tributyl- and triphenyl-tin chloride, bis -(tri- n -butyltin) oxide and triphenyltin hydroxide. Mössbauer spectra were recorded for the resultant interactions of the species produced with the various sediments. The Mössbauer spectra of both types of sediment, aerobic and anaerobic, spiked with tributyltin chloride and bis -(tri- n -butyltin) oxide were the same, suggesting that these compounds were converted to the same species, mostly likely the hydrated tributyltin cation, TBT+. The spectra of all triphenyltin chloride and triphenyltin hydroxide spiked sediment samples were the same, indicating again that these compounds were converted to the same species, in this case the hydrated triphenyltin cation, TPT+. Thus the species that interacts with the various sediments are the respective hydrated cations. The results also support the previous conclusion obtained with Chesapeake Bay sediments, that the product of triorganotin speciation depends on the nature of sediment. Copyright © 2001 John Wiley & Sons, Ltd. [source]

Synthesis of MnGeO3 polycrystalline and single-crystal samples and comparative analysis of their magnetic properties

N. V. Sapronova
Abstract MnGeO3 single crystals have been grown by a flux method. The obtained MnGeO3 is orthorhombic; a Pbca space group does not undergo any structural phase transitions in the range from room temperature to 900 °C. Magnetic measurements carried out for the first time on the MnGeO3 single crystal have revealed higher values (TN = 38 K and , = ,100 K) as compared to the data for polycrystalline samples reported in the literature (TN = 10 K and 14 K, , = ,54 K and ,46 K). These magnetic parameters for polycrystalline samples synthesized by us are close to the literature data. A Mössbauer spectrum taken at T = 300 K for a sample containing 5% Fe257O3 shows that manganese ions, Mn2+, occupy two nonequivalent positions and iron is included in a sublattice as Fe2+ and distributed among two positions substituting Mn2+. In this study, the magnetic characteristics are shown to be sensitive even to minor impurity amounts. The MnGeO3 magnetic structure and one of possible reasons causing the effect of impurities on the MnGeO3 magnetic properties are considered in the framework of a simple indirect coupling model. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Temperature-dependent crystal structure refinement and 57Fe Mössbauer spectroscopy of Cu2Fe2Ge4O13

Günther J. Redhammer
The germanate compound Cu2Fe2Ge4O13, dicopper diiron germanate, was synthesized by solid-state reaction at 1403,K and ambient pressure. There is no change of space-group symmetry between 10 and 900,K. Between 40,K and room temperature the a lattice parameter shows a negative thermal expansion which can be connected to a decreasing Cu,Cu interatomic distance. Above room temperature all the lattice parameters are positively correlated with temperature. Among the structural parameters several alterations with temperature occur, which are most prominent for the distorted Fe3+ octahedral site. Besides an increase of the average bond length and of the interatomic Fe,Fe distances, distortional parameters also increase with temperature, while the average Cu,O bond length remains almost constant between 100 and 900,K, as do the average Ge,O distances. 57Fe Mössbauer spectroscopy was used to detect long-range magnetic ordering in Cu2Fe2Ge4O13. While around 100,K, which is the temperature at which a broad maximum is observed in the magnetic susceptibility, no magnetic ordering was detected in the Mössbauer spectrum, below 40,K a narrow split sextet is developed which is indicative of a three-dimensional magnetic ordering of the sample. [source]

Manganoan rockbridgeite Fe4.32Mn0.62Zn0.06(PO4)3(OH)5: structure analysis and 57Fe Mössbauer spectroscopy

Günther J. Redhammer
The structure of the basic iron phosphate rockbridgeite [iron manganese zinc tris­(phosphate) penta­hydroxide] was reinvestigated with special emphasis on the cation distribution deduced from new X-ray and 57Fe Mössbauer data. Rockbridgeite is orthorhombic, space group Cmcm, and shows three different Fe sites, one with symmetry, another with m symmetry and the third in a general position. One phosphate group has the P atom on a site with m symmetry, while the other has the P atom at a site with mm symmetry. Two Fe sites are fully occupied by ferric iron, while Mn3+ and Fe2+ are situated at a third, principally Fe, site. Structural data, bond-valence sums and polyhedral distortion parameters suggest a new inter­pretation of the rockbridgeite 57Fe Mössbauer spectrum. [source]