Np(IV)/Np(V) valence determinations from Np L3 edge XANES/EXAFS

X-ray absorption near edge structure (XANES) spectroscopy for in situ metal valence determination has become a powerful analytical tool in heterogeneous systems. This is in part because it is applicable without prior separation procedures. For some systems, however, determining the oxidation state from XANES spectra is not straightforward and caution must be used. We show that the analysis of L3,2 edge EXAFS (extended X-ray absorption fine structure) spectra is better suited to distinguish between Np(IV) and Np(V) than from their XANES spectra. Whereas evidence for the oxidation of Np(IV) in solution samples from their Np L3 XANES is unclear, their EXAFS data unequivocally reveals Np(V) formation in the solutions.     

Structural insights into nonheme alkylperoxoiron(III) and oxoiron(IV) intermediates by X-ray absorption spectroscopy

Transient mononuclear low-spin alkylperoxoiron(III) and oxoiron(IV) complexes that are relevant to the activation of dioxygen by nonheme iron enzymes have been generated from synthetic iron(II) complexes of neutral tetradentate (TPA) and pentadentate (N4Py, Bn-TPEN) ligands and structurally characterized by means of Fe K-edge X-ray absorption spectroscopy (XAS). Notable features obtained from fits of the EXAFS region are Fe-O bond lengths of 1.78 A for the alkylperoxoiron(III) intermediates and 1.65-1.68 A for the oxoiron(IV) intermediates, reflecting different strengths in the Fe-O pi interactions. These differences are also observed in the intensities of the 1s-to-3d transitions in the XANES region, which increase from 4 units for the nearly octahedral iron(II) precursor to 9-15 units for the alkylperoxoiron(III) intermediates to 25-29 units for the oxoiron(IV) species.     

X-ray absorption spectroscopy study of H2S sorption on iron-rich soil: characterization of iron-sulfur species

Iron-rich soil after sorption of H(2)S was characterized using X-ray absorption near-edge structural (XANES) and extended X-ray absorption fine structure spectroscopy (EXAFS) for determination the possible products in the present work. EXAFS revealed that the main Fe-S species in the sulfided sample were FeS (troilite) and Fe(1-x)S (pyrrohotite). Iron in the sulfided sample was found to possess a Fe-S bond distance of 2.36 A and a Fe-O bond distance of 1.72 A in the Fe-K-edge spectra whereas the Fe-S bond distance of 2.25 A was determined in the sulfur K-edge spectra. In the second shells, the bond distance of Fe-O-Si or Fe-O-Al with 3.28 A was also observed. No FeS2 (pyrite) was included in the sulfided sample. The formation of Fe(1-x)S was probably attributed to the presence of Fe(3)O(4), a type of spinel structure with a lattice deficiency.     

Surface arsenic speciation of a drinking-water treatment residual using X-ray absorption spectroscopy

Drinking-water treatment residuals (WTRs) present a low-cost geosorbent for As-contaminated waters and soils. Previous work has demonstrated the high affinity of WTRs for As, but data pertaining to the stability of sorbed As is missing. Sorption/desorption and X-ray absorption spectroscopy (XAS), both XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) studies, were combined to determine the stability of As sorbed by an Fe-based WTR. Arsenic(V) and As(III) sorption kinetics were biphasic in nature, sorbing >90% of the initial added As (15,000 mg kg(-1)) after 48 h of reaction. Subsequent desorption experiments with a high P load (7500 mg kg(-1)) showed negligible As desorption for both As species, approximately <3.5% of sorbed As; the small amount of desorbed As was attributed to the abundance of sorption sites. XANES data showed that sorption kinetics for either As(III) or As(V) initially added to solution had no effect on the sorbed As oxidation state. EXAFS spectroscopy suggested that As added either as As(III) or as As(V) formed inner-sphere mononuclear, bidentate complexes, suggesting the stability of the sorbed As, which was further corroborated by the minimum As desorption from the Fe-WTR.     

X-ray absorption spectroscopy of hemes and hemeproteins in solution: multiple scattering analysis

A full quantitative analysis of Fe K-edge X-ray absorption spectra has been performed for hemes in two porphynato complexes, that is, iron(III) tetraphenylporphyrin chloride (Fe(III)TPPCl) and iron(III) tetraphenylporphyrin bis(imidazole) (Fe(III)TPP(Imid)2), in two protein complexes whose X-ray structure is known at atomic resolution (1.0 A), that is, ferrous deoxy-myoglobin (Fe(II)Mb) and ferric aquo-myoglobin (Fe(III)MbH2O), and in ferric cyano-myoglobin (Fe(III)MbCN), whose X-ray structure is known at lower resolution (1.4 A). The analysis has been performed via the multiple scattering approach, starting from a muffin tin approximation of the molecular potential. The Fe-heme structure has been obtained by analyzing independently the Extended X-ray Absorption Fine Structure (EXAFS) region and the X-ray Absorption Near Edge Structure (XANES) region. The EXAFS structural results are in full agreement with the crystallographic values of the models, with an accuracy of +/- 0.02 A for Fe-ligand distances, and +/-6 degrees for angular parameters. All the XANES features above the theoretical zero energy (in the lower rising edge) are well accounted for by single-channel calculations, for both Fe(II) and Fe(III) hemes, and the Fe-N p distance is determined with the same accuracy as EXAFS. XANES evaluations of Fe-5th and Fe-6th ligand distances are determined with 0.04-0.07 A accuracy; a small discrepancy with EXAFS (0.01 to 0.05 A beyond the statistical error), is found for protein compounds. Concerns from statistical correlation among parameters and multiple minima in the parameter space are discussed. As expected, the XANES accuracy is slightly lower than what was found for polarized XANES on Fe(III)MbCN single crystal (0.03-0.04 A), and states the actual state-of-the-art of XANES analysis when used to extract heme-normal parameters in a solution spectrum dominated by heme-plane scattering.     

Structural and physical characterization of tetranuclear [Mn(II)3Mn(IV)] and [Mn(II)2Mn(III)2] valence-isomer manganese complexes

Two tetranuclear Mn complexes with an average Mn oxidation state of +2.5 have been prepared. These valence isomers have been characterized by a combination of X-ray crystallography, X-ray absorption spectroscopy, and magnetic susceptibility. The Mn(II)3Mn(IV) tetramer has the Mn ions arranged in a distorted tetrahedron, with an S = 6 ground spin state, dominated by ferromagnetic exchange among the manganese ions. The Mn(II)2Mn(III)2 tetramer also has a distorted tetrahedral arrangement of Mn ions but shows magnetic behavior, suggesting that it is a single-molecule magnet. The X-ray absorption near-edge structure (XANES) spectra for the two complexes are similar, suggesting that, while Mn XANES has sufficient sensitivity to distinguish between trinuclear valence isomers (Alexiou et al. Inorg. Chem. 2003, 42, 2185), similar distinctions are difficult for tetranuclear complexes such as that found in the photosynthetic oxygen-evolving complex.     

Redox chemistry of tantalum clusters on silica characterized by X-ray absorption spectroscopy

SiO(2)-supported clusters of tantalum were synthesized from adsorbed Ta(CH(2)Ph)(5) by treatment in H(2) at 523 K. The surface species were characterized by X-ray absorption spectroscopy (extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES)) and ultraviolet-visible spectroscopy. The EXAFS data show that SiO(2)-supported tantalum clusters were characterized by a Ta-Ta coordination number of approximately 2, consistent with the presence of tritantalum clusters, on average. When these were reduced in H(2) and reoxidized in O(2), the cluster nuclearity remained essentially unchanged, although reduction and oxidation occurred, respectively, as shown by XANES and UV-vis spectra; in the reoxidation, the tantalum oxidation state change was approximately two electronic charges per tritantalum cluster. The data demonstrate an analogy between the chemistry of group 5 metals on the SiO(2) support and their chemistry in solution, as determined by the group of Cotton.     

Picosecond X-ray absorption spectroscopy of a photoinduced iron(II) spin crossover reaction in solution

In this study, we perform steady-state and time-resolved X-ray absorption spectroscopy (XAS) on the iron K-edge of [Fe(tren(py)3)](PF6)2 dissolved in acetonitrile solution. Static XAS measurements on the low-spin parent compound and its high-spin analogue, [Fe(tren(6-Me-py)3)](PF6)2, reveal distinct spectroscopic signatures for the two spin states in the X-ray absorption near-edge structure (XANES) and in the X-ray absorption fine structure (EXAFS). For the time-resolved studies, 100 fs, 400 nm pump pulses initiate a charge-transfer transition in the low-spin complex. The subsequent electronic and geometric changes associated with the formation of the high-spin excited state are probed with 70 ps, 7.1 keV, tunable X-ray pulses derived from the Advanced Light Source (ALS). Modeling of the transient XAS data reveals that the average iron-nitrogen (Fe-N) bond is lengthened by 0.21+/-0.03 A in the high-spin excited state relative to the ground state within 70 ps. This structural modification causes a change in the metal-ligand interactions as reflected by the altered density of states of the unoccupied metal orbitals. Our results constitute the first direct measurements of the dynamic atomic and electronic structural rearrangements occurring during a photoinduced FeII spin crossover reaction in solution via picosecond X-ray absorption spectroscopy.     

Electron transfer mechanism and photochemistry of ferrioxalate induced by excitation in the charge transfer band

The photoredox reaction of ferrioxalate after 266/267 nm excitation in the charge transfer band has been studied by means of ultrafast extended X-ray absorption fine structure (EXAFS) analysis, optical transient spectroscopy, and quantum chemistry calculations. The Fe-O bond length changes combined with the transient spectra and kinetics have been measured and in combination with ultrahigh frequency density functional theory (UHF/DFT) calculations are used to determine the photochemical mechanism for the Fe(III) to Fe(II) redox reaction. The present data and the results obtained with 266/267 nm excitations strongly suggest that the primary reaction is the dissociation of the Fe-O bond before intramolecular electron transfer occurs. Low quantum yield electron photodetachment from ferrioxalate has also been observed.     

Molecular scale speciation of first-row transition elements bound to ligneous material by using X-ray absorption spectroscopy

To develop a solid scientific basis for maintaining soil quality and formulating effective remediation strategies, it is critical to determine how environmentally-important trace metals are sequestered in soils at the molecular scale. The speciation of Mn, Fe and Cu in soil organic matter has been determined by synchrotron-based techniques: extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES). We show the structural similarity between the surface complexes of Mn(II), Fe(III) and Cu(II). These cations are bound to the surface through oxygen atoms. Each one presents a more or less tetragonal-distorted octahedral geometry. The use of X-ray absorption spectroscopy provides a relevant method for determining trace-metal speciation in both natural and contaminated environmental materials.     

Synthesis, characterization, and physicochemical properties of manganese(III) and manganese(V)-oxo corrolazines

The structural and physicochemical properties of the manganese-corrolazine (Cz) complexes (TBP8Cz)Mn(V)O (1) and (TBP8Cz)Mn(III) (2) (TBP = p-tert-butylphenyl) have been determined. Recrystallization of 2 from toluene/MeOH resulted in the crystal structure of (TBP8Cz)Mn(III)(CH3OH) (2 x MeOH). The packing diagram of 2 x MeOH reveals hydrogen bonds between MeOH axial ligands and meso N atoms of adjacent molecules. Solution binding studies of 2 with different axial ligands (Cl-, Et3PO, and Ph3PO) reveal strong binding, corroborating the preference of the Mn(III) ion for a five-coordinate environment. High-frequency and field electron paramagnetic resonance (HFEPR) spectroscopy of solid 2 x MeOH shows that 2 x MeOH is best described as a high-spin (S = 2) Mn(III) complex with zero-field splitting parameters typical of corroles. Structural information on 1 was obtained through an X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) study and compared to XANES/EXAFS data for 2 x MeOH. The XANES data for 1 shows an intense pre-edge transition characteristic of a high-valent metal-oxo species, and a best fit of the EXAFS data gives a short Mn-O bond distance of 1.56 A, confirming the structure of the metal-oxo unit in 1. Detailed spectroelectrochemical studies of 1 and 2 were performed revealing multiple reversible redox processes for both complexes, including a relatively low potential for the Mn(V) --> Mn(IV) process in 1 (near 0.0 V vs saturated calomel reference electrode). Chemical reduction of 1 results in the formation of a Mn(III)Mn(IV)(mu-O) dimer as characterized by electron paramagnetic resonance spectroscopy.     

Structure of iron and manganese ions substituted in the framework of nanoporous AlPO-5 material

The structure of iron and managanese ions substituted in the framework of nanoporous AlPO-5 is determined by ex situ and in situ X-ray absorption spectroscopy. Fe K-edge XANES and EXAFS studies clearly indicate that iron ions are present as Fe(III) in octahedral coordination in the assynthesised material and tetrahedral coordination in the calcined material in both pure FeAlPO-5 and FeMnalPO-5. XANES and EXAFS results also indicate that reaction with hydrogen peroxide causes the removal of Fe(III) ions from the framework. Mn K-edge XANES and EXAFS of FeMnAlPO-5 samples indicate that Mn(II) ions are present in the framework, tetrahedrally coordinated, in the as-synthesised material but upon calcination it is found that the Mn(II) ions are removed from the framework, suggesting a different synthesis strategy is necessary to stabilise the Mn(II) ions in the framework simultaneously with Fe(III) ions.     

X-ray absorption spectroscopy to analyze nuclear geometry and electronic structure of biological metal centers—potential and questions examined with special focus on the tetra-nuclear manganese complex of oxygenic photosynthesis

X-ray absorption spectroscopy (XAS) has become a prominent tool for the element-specific analysis of transition metals at the catalytic center of metalloenzymes. In the present study the information content of X-ray spectra with respect to the nuclear geometry and, in particular, to the electronic structure of the protein-bound metal ions is explored using the manganese complex of photosystem II (PSIII) as a model system. The EXAFS range carries direct information on the number and distances of ligands as well as on the chemical type of the ligand donor function. For first-sphere ligands and second-sphere metals (in multinuclear complexes), the determination of precise distances is mostly straightforward, whereas the determination of coordination numbers clearly requires more effort. The EXAFS section starts with an exemplifying discussion of a PSII spectrum data set with focus on the coordination number problem. Subsequently, the method of linear dichroism EXAFS spectroscopy is introduced and it is shown how the EXAFS data leads to an atomic resolution model for the tetra-manganese complex of PSII. In the XANES section the following aspects are considered: (1) Alternative approaches are evaluated for determination of the metal-oxidation state by comparison with a series of model compounds. (2) The interpretation of XANES spectra in terms of molecular orbitals (MOs) is approached by comparative multiple-scattering calculations and MO calculations. (3) The underlying reasons for the oxidation-state dependence of the XANES spectra are explored. Furthermore, the potential of modern XANES theory is demonstrated by presenting first simulations of the dichroism in the XANES spectra of the PSII manganese complex.     

Structural investigation of high-valent manganese-salen complexes by UV/Vis,Raman, XANES,and EXAFS spectroscopy

XANES and EXAFS spectroscopic studies at the Mn-K- and Br-K-edge of reaction products of (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride ([(salen)Mn(III)Cl], 1) and (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) bromide ([(salen)Mn(III)Br], 2) with 4-phenylpyridine N-oxide (4-PPNO) and 3-chloroperoxybenzoic acid (MCPBA) are reported. The reaction of the Mn(III) complexes with two equivalents of 4-PPNO leads to a hexacoordinated compound, in which the manganese atom is octahedrally coordinated by four oxygen/nitrogen atoms of the salen ligand at an average distance of approximately 1.90 A and two additional, axially bonded oxygen atoms of the 4-PPNO at 2.25 A. The oxidation state of this complex was determined as approximately +IV by a comparative study of Mn(III) and Mn(V) reference compounds. The green intermediate obtained in reactions of MCPBA and solutions of 1 or 2 in acetonitrile was investigated with XANES, EXAFS, UV/Vis, and Raman spectroscopy, and an increase of the coordination number of the manganese atoms from 4 to 5 and the complete abstraction of the halide was observed. A formal oxidation state of IV was deduced from the relative position of the pre-edge 1s-->3d feature of the X-ray absorption spectrum of the complex. The broad UV/Vis band of this complex in acetonitrile with lambda(max)=648 nm was consistent with a radical cation structure, in which a MCPBA molecule was bound to the Mn(IV) central atom. An oxomanganese(V) or a dimeric manganese(IV) species was not detected.     

Structural characterization study of FeCo alloy nanoparticles in a highly porous aerogel silica matrix

A series of FeCo-SiO(2) nanocomposite aerogels having different FeCo loadings of 3, 5, and 8 wt % were prepared using a novel urea-assisted sol-gel route. The size of the nanoparticles, which was estimated using Scherrer analysis of the main peak of the x-ray diffraction pattern, varies from 3 to 8 nm. X-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) techniques at both Fe and Co K edges were used to investigate the structure of the FeCo nanoparticles. EXAFS and XANES show that FeCo nanoparticles have the typical bcc structure. Evidence of oxidation was observed in low FeCo content aerogels. Spatially resolved electron energy loss spectroscopy analysis suggests the formation of a passivation layer of predominantly iron oxide.     

Determination of CoSi2 self-aligned nanostructures with grazing incidence X-ray absorption spectroscopy

Self-aligned nanostructures (SAN) made by reacting Co nanoparticles with crystalline Si substrates at high temperatures were studied with grazing incidence X-ray absorption spectroscopy (GI-XAS). The results from extended X-ray absorption fine structure (EXAFS) analysis and X-ray absorption near-edge spectroscopy (XANES) were used to identify SAN as crystalline CoSi2. Theoretical calculations of EXAFS and XANES spectra of several crystalline cobalt silicides were performed with the FEFF8 package. On the basis of these studies, the SAN samples were determined to contain nearly pure CoSi2.     

Solvation of Copper(II) Ions in Liquid Ammonia

X-ray absorption fine structure (XAFS) measurements have been performed at -50 degrees C on a 0.4 mol dm(-)(3) copper(II) nitrate solution in liquid ammonia. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the coordination number and bond distances for the solvated copper(II) ion in solution. The equatorial ammonia nitrogens are located 2.00 ? from the copper and the axial nitrogen 2.19 ? from the copper. However, it was not possible from the EXAFS analysis alone to conclude whether there was one or two axial nitrogens. Therefore, X-ray absorption near-edge structure (XANES) spectroscopy was combined with discrete variational Xalpha (DV-Xalpha) molecular orbital calculations for a series of five- and six-coordinated models to determine the coordination number and the geometry. The experimental XANES spectrum was best reproduced by a model where the copper(II) ion is pentacoordinated in liquid ammonia in a square pyramidal geometry with the copper(II) ion lifted above the average nitrogen plane.     

An X-ray absorption spectroscopic study on mixed conductive La0.6Sr0.4Co0.8Fe0.2O(3-δ) cathodes. I. Electrical conductivity and electronic structure

The electrical conduction mechanism of mixed conductive perovskite oxides, La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ), for cathode materials of solid oxide fuel cells has been investigated from electronic structural changes during oxygen vacancy formation. La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ) was annealed under various oxygen partial pressures p(O(2))s at 1073 K and quenched. Iodometric titration indicated that the oxygen nonstoichiometry of La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ) depended on the annealing p(O(2)), with more oxygen vacancies introduced at lower than at higher p(O(2))s. X-Ray absorption spectroscopic measurements were performed at the O K-, Co L-, Fe L-, Co K-, and Fe K-edges. The valence states of the Co and Fe ions were investigated by the X-ray absorption near edge structure (XANES) at the Co and Fe L(III)-edges. While the Fe average valence was almost constant, the valence of the Co ions decreased with oxygen vacancy introduction. The O K-edge XANES spectra indicated that electrons were injected into the Co 3d/O 2p hybridization state with oxygen vacancy introduction. Both absorption edges at the Co and Fe K-edge XANES shifted towards lower energies with oxygen vacancy introduction. The shift at the Co K-edge resulted from the decrease in the Co average valence and that at the Fe K-edge appeared to be caused by changes in the coordination environment around the Fe ions. The total conductivity of La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ) decreased with decreasing p(O(2)), due to a decreasing hole concentration.     

Synthesis and reactivity of dimethyl gold complexes supported on MgO: characterization by infrared and X-ray absorption spectroscopies

Dimethyl gold complexes bonded to partially dehydroxylated MgO powder calcined at 673 K were synthesized by adsorption of Au(CH3)2(acac) (acac is C5H7O2) from n-pentane solution. The synthesis and subsequent decomposition of the complexes by treatment in He or H2 were characterized with diffuse reflectance Fourier transform infrared (DRIFT), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopies. The XANES results identify Au(III) in the supported complexes, and the EXAFS and DRIFTS data indicate mononuclear dimethyl gold complexes as the predominant surface gold species, consistent with the lack of Au-Au contributions in the EXAFS spectrum and the presence of nu(as)(CH3) and nu(s)(CH3) bands in the IR spectrum. EXAFS data show that each complex is bonded to two oxygen atoms of the MgO surface at an Au-O distance of 2.16 angstroms. The DRIFT spectra show that reaction of Au(CH3)2(acac) with MgO at room temperature also formed Mg(acac)2 and H(acac) species on the support. Treatment of the dimethyl gold complexes in He or H2 at increasing temperatures varying from 373 to 573 K removed CH3 ligands and caused aggregation forming zerovalent gold nanoclusters of increasing size, ultimately with an average diameter of about 30 angstroms. Analysis of the gas-phase products during the genesis of the gold clusters indicated formation of CH4 (consistent with removal of CH3 groups) and CO2 at 473-573 K, associated with decomposition of the organic ligands derived from acac species. O2 and CO2 were also formed in the decomposition of ubiquitous carbonates present on the surface of the MgO support.     

A solution study on the local and global structure changes of cytochrome c: an unfolding process induced by urea

The local and global structural changes of cytochrome c induced by urea in aqueous solution have been studied using X-ray absorption spectroscopy (XAS) and small-angle X-ray scattering (SAXS). According to the XAS result, both the native (folded) protein and the unfolded protein exhibit the same preedge features taken at Fe K-edge, indicating that the Fe(III) in the heme group of the protein maintains a six-coordinated local structure in both the folded and unfolded states. Furthermore, the discernible differences in the X-ray absorption near-edge structure (XANES) of these two states are attributed to a possible spin transition of the Fe(III) from a low-spin state to a high-spin state during the unfolding process. The perseverance of six-coordination and the spin transition of the iron are reconciled by a proposed ligand exchange, with urea and water molecules replacing the methionine-80 and histidine-18 axial ligands, respectively. The SAXS result reveals a significant morphology change of cytochrome c from a globular shape of a radius of gyration R(g) = 12.8 A of the native protein to an elongated ellipsoid shape of R(g) = 29.7 A for the unfolded protein in the presence of concentrated urea. The extended X-ray absorption fine structure (EXAFS) data unveil the coordination geometries of Fe(III) in both the folded and unfolded state of cytochrome c. An initial spin transition of Fe(III) followed by an axial ligand exchange, accompanied by the change in the global envelope, is proposed for what happened in the protein unfolding process of cytochrome c.