Inorganic Chemistry

Published by American Chemical Society
Online ISSN: 1520-510X
Print ISSN: 0020-1669
The complexes [Ni(S2C2Me2)2](z) (z = 0, 1-, 2-) have been isolated for the purpose of investigating their electronic structures in a reversible three-member electron-transfer series. Members are interrelated by reversible redox reactions with E(1/2)(0/1-) = -0.15 V and E(1/2)(1-/2-) = -1.05 V versus SCE in acetonitrile. The three complexes have nearly planar structures of idealized D(2)(h) symmetry. As the series is traversed in the reducing direction, Ni-S and C-S bond lengths increase; the chelate ring C-C bond length decreases from the neutral complex to the monoanion and does not change significantly in the dianion. Structural trends are compared with previous results for [Ni(S2C2R2)2)](1-,2-). Following the geometrical changes, values of nu(Ni)(-)(S) and nu(C)(-)(S) decrease, while the value of nu(C)(-)(C) increases with increased reduction. Geometry optimizations at the density functional theory (DFT) level were performed for all members of the series. Geometrical parameters obtained from the calculations are in good agreement with the experimental findings. The 5b(2g) orbital was identified as the LUMO in [Ni(S2C2Me2)2], the SOMO in [Ni(S2C2Me2)2](1-), and the HOMO in [Ni(S2C2Me2)2]2-. Unlike in the situation in the [M(CO)2-(S2C2Me2)2]z series (M = Mo, W; z = 0, 1-, 2-), the apparent contribution from the metal d orbital in the electroactive orbital is not constant. In the present series, the d(xz) contribution increases from 13 to 20 to 39% upon passing from the neutral to the monoanionic to the dianionic complex. Accurate calculation of EPR g-values of [Ni(S2C2Me2)2]1- by DFT serves as a test for the reliability of the electronic structure calculations.
The reaction of ReCl(5) with 3 equiv of a benzene-1,2-dithiolate derivative in CH(3)CN produced, after the addition of [C(8)H(16)N]Br ([C(8)H(16)N](+) is 5-azonia-spiro[4,4]nonane), brownish-green crystals of [C(8)H(16)N][Re(tms)(3)] (1c) and [C(8)H(16)N][Re(Cl(2)-bdt)(3)] (2c), where (tms)(2-) represents 3,6-bis(trimethylsilyl)benzene-1,2-dithiolate and (Cl(2)-bdt)(2-) is 3,6-dichlorobenzene-1,2-dithiolate. Chemical reduction of [Re(bdt)(3)] (3b) with n-butyllithium in the presence of PPh(4)Br yielded [PPh(4)][Re(bdt)(3)] (3c), where (bdt)(2-) is benzene-1,2-dithiolate. The three monoanionic complexes possess a diamagnetic ground state (Re(V), d(2), S = 0). The crystal structures of 1c x 2 CH(3)CN and 2c x C(3)H(6)O have been determined by X-ray crystallography. The electrochemistry establishes that the complexes are members of electron transfer series involving a monocation [Re(V)(L(*))(2)(L)](+) (S = 0(?)), a neutral [Re(V)(L(*))(L)(2)](0) (S = 1/2), a monoanion [Re(V)(L)(3)](1-) (S = 0), a dianion [Re(IV)(L)(3)](2-) (S = 1/2), and a trianion [Re(III)(L)(3)](3-) (S = 1(?)). The unique X-band EPR spectrum of the neutral species clearly describes a diamagnetic Re(V) d(2) central ion with the unpaired electron located in a purely ligand-centered molecular orbital, whereas it is metal-centered in the dianionic form: a Re(IV) d(3) ion with three dithiolate(2-) ligands. S K-edge and Re L-edge X-ray absorption spectroscopy confirms these assignments and furthermore shows that the monoanion has a Re(V) central ion with three dianionic ligands. The geometrical and electronic structures of all members of the electron transfer series have been calculated by density functional theoretical methods, and the S K-pre-edge spectra have been simulated and assigned using a time-dependent DFT protocol.
Sr2FeMnO5+y synthesized in both argon (y = 0) and air (y = 0.5) has a disordered perovskite structure, with random distribution of oxygen vacancies, while Ca2FeMnO5+y synthesized under the same conditions has brownmillerite long-range ordering of O-vacancies. Local ordering of oxygen vacancies exists in Sr2FeMnO5+y as NPDF results point to a brownmillerite-like local structure for Sr2FeMnO5.0. Remarkably, Sr2FeMnO5.0 oxidizes spontaneously in air at room temperature. While Ca2FeMnO5 is a G-type antiferromagnetic below 407K, no long-range order is found for Sr2FeMnO5+y.
In our continued exploratory synthesis of compounds containing transition-metal oxide magnetic nanostructures, a new copper(II) phosphate phase, Cs2Cu3P4O14 (1), was isolated employing the mixed CsCl/2CsI molten flux. The X-ray single-crystal structural analysis shows that the Cs2Cu3P4O(14) phase crystallizes in a monoclinic space group with a = 7.920(2) A, b = 10.795(2) A, c = 7.796(2) A, beta = 103.90(3) degrees , and V = 646.9(2) A(3); P2(1)/c (No. 14); Z = 2. The structure has been refined by the full-matrix least-squares method to a final solution with R1 = 0.0248, wR2 = 0.0553, and GOF = 1.02. The three-dimensional Cu-O-P framework exhibits pseudo-one-dimensional channels where the Cs+ cations reside. The framework consists of trimeric CuO4 square-planar units stacked in a staggered configuration. These CuO4 trimers are interlinked by the P2O7 units via vertex-sharing O atoms. The stacked CuO4 units are slanted with respect to the Cu...Cu...Cu vector, resulting in additional Cu-O long bonds, 2.71(1) A, and a possibly shortened Cu...Cu distance, 3.38(3) A. 1 shows limited cation substitution with smaller alkali-metal cations; in fact, only a relatively small concentration of Cs+ can be substituted by Rb+ to form Cs(2-x)RbxCu3P4O14 (0.0 </= x </= 0.8). The temperature-dependent magnetic susceptibility studies of 1 and its Rb-substituted analogues (x = 0, 0.33, 0.50, and 0.80) reveal a weak ferromagnetic transition at Tc = approximately 14 K, which evidently is independent of the variation of x. In this paper, we report the synthesis, structure, and properties of the title compounds, as well as its brief comparison with the previously discovered Li2Cu3Si4O12 phase, which exhibits fused square-planar CuO4 trimers.
The Gd2-xCexZr2-xAlxO7 (0.0 ≤ x ≤ 2.0) series was synthesized by the gel combustion method. This system exhibited the presence of a fluorite-type phase, along with a narrow biphasic region, depending upon the Ce/Gd content in the sample. Thermal stability of these new compounds under oxidizing and reducing conditions has been investigated. The products obtained on decomposition of Gd2-xCexZr2-xAlxO7 in oxidizing and reducing conditions were found to be entirely different. It was observed that in air the fluorite-type solid solutions of Gd2-xCexZr2-xAlxO7 composition undergo phase separation into perovskite GdAlO3 and fluorite-type solid solutions of Gd-Ce-Zr-O or Ce-Zr-Al-O depending upon the extent of Ce and Al substitution. On the other hand, Gd2-xCexZr2-xAlxO7 samples on heating under reducing conditions show a phase separation to CeAlO3 perovskite and a defect-fluorite of Gd2Zr2O7. The extent of metastability for a typical composition of Gd1.2Ce0.8Zr1.2Al0.8O7 (nano), Gd1.2Ce0.8Zr1.2Al0.8O6.6 (heated under reduced conditions), Gd1.2Ce0.8Zr1.2Al0.8O7 (heated in air at 1200 °C) has been experimentally determined employing a high temperature Calvet calorimeter. On the basis of thermodynamic stability data, it could be inferred that the formation of a more stable compound in the presence of two competing cations (i.e., Gd(3+) and Ce(3+)) is guided by the crystallographic stability.
A new series of La(1-x)Ce(x)CrO(3) (0.0 <or= x <or=1.0) compounds in nanocrystalline form were synthesized using a two-step synthesis route, involving an initial combustion reaction followed by vacuum heating in the presence of a Zr sponge, which acted as an oxygen getter. For the first time, a homogeneous solid solution formation throughout the entire range was obtained in this series. These compounds were characterized using X-ray diffraction, diffuse reflectance UV visible spectrophotometry, and superconducting quantum interference device magnetometry. The crystallite size for the phase-pure products was confirmed to be approximately 42-44 nm by high-resolution transmission electron microscopy. All compounds (nanocrystalline) in this series are found to be predominantly antiferromagnetic in nature with a remarkable linear increasing trend in Neel temperature from 257 to 281.5 K as a function of decreasing Ce(3+) content. Interestingly, the band gap also shows a linear decrease from 3.21 to 3.02 eV as a function of increasing Ce(3+) concentration in the La(1-x)Ce(x)CrO(3) series.
Detailed structural and electrical investigations were carried out on an A-site disordered hexagonal Y1-xGdxInO3 (0.0 ≤ x ≤ 1.0) series synthesized by a self-assisted gel-combustion route. The phase relations show profound temperature dependence. The metastable C-type modification could be stabilized for all the compositions, which on further heating get converted to stable hexagonal polymorphs. The conversion temperature (C-type to hexagonal) was found to increase with an increase in Y(3+) content. The system was observed to be single-phasic hexagonal at 1250 °C throughout the composition range. Interestingly, the increase in planar bonds of InO5 polyhedra was found to be twice that of the apical bonds on Gd(3+) substitution. Careful Raman spectroscopic studies highlighted a definitive though subtle structural change from x = 0.7 onward. The same observation is also corroborated by the dielectric studies. Electric field-dependent polarization measurements showed the ferroelectric hysteresis loop for pure YInO3. The system transforms from ferroelectric in YInO3 to almost paraelectric for GdInO3. In the present study, XRD, Raman, and electrical characterizations in conjunction reveal that to tune the electrical properties of the hexagonal rare earth indates, the variation in tilting of InO5 polyhedra has to be influenced, which could not be brought about by isovalent A-site substitution.
A new perovskite cathode, Sr0.95Ce0.05CoO3-δ, performs well for oxygen-reduction reactions in solid oxide fuel cells (SOFCs). We gain insight into the crystal structure of Sr1-xCexCoO3-δ (x = 0.05, 0.1) and temperature-dependent structural evolution of Sr0.95Ce0.05CoO3-δ by X-ray diffraction, neutron powder diffraction, and scanning transmission electron microscopy experiments. Sr0.9Ce0.1CoO3-δ shows a perfectly cubic structure (a = a0), with a large oxygen deficiency in a single oxygen site; however, Sr0.95Ce0.05CoO3-δ exhibits a tetragonal perovskite superstructure with a double c axis, defined in the P4/mmm space group, that contains two crystallographically different cobalt positions, with distinct oxygen environments. The structural evolution of Sr0.95Ce0.05CoO3-δ at high temperatures was further studied by in situ temperature-dependent NPD experiments. At 1100 K, the oxygen atoms in Sr0.95Ce0.05CoO3-δ show large and highly anisotropic displacement factors, suggesting a significant ionic mobility. The test cell with a La0.8Sr0.2Ga0.83Mg0.17O3-δ-electrolyte-supported (∼300 μm thickness) configuration yields peak power densities of 0.25 and 0.48 W cm(-2) at temperatures of 1023 and 1073 K, respectively, with pure H2 as the fuel and ambient air as the oxidant. The electrochemical impedance spectra evolution with time of the symmetric cathode fuel cell measured at 1073 K shows that the Sr0.95Ce0.05CoO3-δ cathode possesses superior ORR catalytic activity and long-term stability. Mixed ionic-electronic conduction properties of Sr0.95Ce0.05CoO3-δ account for its good performance as an oxygen-reduction catalyst.
The multi-walled and bamboo-like well-crystalline CNx nanotubes with controllable nitrogen concentration (x = 0.05-1.02) were synthesized. The stoichiometry of as-prepared CNx (x congruent with 1.02) is close to that of the theoretically predicted graphite-like CN.
(Ni(1-x),Mg(x))(3)Si(2)O(5)(OH)(4) solid-solution nanotubes (NTs) with tunable compositions were hydrothermally synthesized by altering the molar ratio of Mg(2+) to Ni(2+). The as-synthesized NTs were loaded with sub-0.06 wt % palladium (Pd; ∼0.045 wt %) for Suzuki-Miyaura (SM) coupling reactions between iodobenzene or 4-iodotoluene and phenylboronic acid. The (Ni,Mg)(3)Si(2)O(5)(OH)(4) (Mg(2+):Ni(2+) = 1.0:1.0) NTs supported by 0.045 wt % Pd promoted the iodobenzene-participated coupling reaction with a high yield of >99%, an excellent recycling catalytic performance during 10 cycles of catalysis with yields of ∼99%, and also an extremely low Pd releasing level of ∼0.02 ppm. High-activity Pd and PdO clusters, multitudes of dislocations, and defects and terraces contained within the NTs should contribute to the (Ni,Mg)(3)Si(2)O(5)(OH)(4) (Mg(2+):Ni(2+) = 1.0:1.0) NTs supported by 0.045 wt % Pd as a robust, reusable, and high-efficiency catalyst for SM coupling reactions with an extremely low Pd releasing level. The present hydrothermally stable (Ni,Mg)(3)Si(2)O(5)(OH)(4) (Mg(2+):Ni(2+) = 1.0:1.0) solid-solution silicate NTs provided an ideal alternative tubular-structured support for noble- or transition-metal catalysts with low Pd loading, good recycling, and extremely low ppb levels of Pd release, which could also be extended to some other SM coupling reactions.
The synthesis, X-ray structure, and EPR measurements of the integer-spin linear-chain antiferromagnet [Ni(ox)(dmiz)2] (where ox = C2O4(2-) and dmiz = 1,2-dimethylimidazole) are presented. The sign and size of the single-ion zero field splitting (Zfs) of the divalent Ni have been determined by high field/high-frequency EPR spectroscopy. The spectra of powder samples of the derivatives [NixZn1-x(C2O4)(dmiz)2] for x = 0.09 and 0.07, at frequencies ranging from 110 to 440 GHz allowed the accurate determination of the zfs parameters D and E, with D = 1.875(4) cm(-1) and E = 0.38 cm(-1). The X-ray structure has been determined from measurements on a single crystal with x = 0.07. Structural parameters are as follows: a = 14.5252(7) A, b = 12.1916(8) A, c = 8.6850(8) A,beta = 97.460(6)degrees in space group C2/c. The zigzag chain contains octahedrally coordinated metal ions with two cis-oriented N-coordinated dmiz ligands and two cis-oriented, tetradentate bridging oxalato(2-) ligands, together resulting in a MN2O4 donor set. The structure was refined to a conventional R value of 0.073 for 1,051 observed reflections. Zn-O distances are 2.167(5) A and Zn-N = 2.098 A. Coordination angles vary for cis angles from 78.4 to 100.7 degrees, with trans angles varying from 163.9 degrees to 165.5 degrees.
A different thermal treatment of identical reactants (EuI2, NaCN, NaN3, and InI) leads to the formation of the three title compounds. In(0.08)Eu4(NCN)3I3 is isotypic with the reported LiEu4(NCN)3I3, Eu8I9(CN)(NCN)3 represents the first mixed cyanide-cyanamide rare-earth compound, and In(0.28)Eu12(NCN)5I(14.91) is characterized by a sandwich-like stacking motif involving Eu4-NCN double layers stuffed by a layer of vertex-sharing InI6 octahedra. The redox behavior of In is the main factor that leads to alternative product formation as a function of the temperature.
Perovskite-type CaMn(1-x)Nb(x)O(3+/-delta) (x = 0.02, 0.05, and 0.08) compounds were synthesized by applying both a "chimie douce" (SC) synthesis and a classical solid state reaction (SSR) method. The crystallographic parameters of the resulting phases were determined from X-ray, electron, and neutron diffraction data. The manganese oxidations states (Mn(4+)/Mn(3+)) were investigated by X-ray photoemission spectroscopy. The orthorhombic CaMn(1-x)Nb(x)O(3+/-delta) (x = 0.02, 0.05, and 0.08) phases were studied in terms of their high-temperature thermoelectric properties (Seebeck coefficient, electrical resistivity, and thermal conductivity). Differences in electrical transport and thermal properties can be correlated with different microstructures obtained by the two synthesis methods. In the high-temperature range, the electron-doped manganate phases exhibit large absolute Seebeck coefficient and low electrical resistivity values, resulting in a high power factor, PF (e.g., for x = 0.05, S(1000K) = -180 microV K(-1), rho(1000K) = 16.8 mohms cm, and PF > 1.90 x 10(-4) W m(-1) K(-2) for 450 K < T < 1070 K). Furthermore, lower thermal conductivity values are achieved for the SC-derived phases (kappa < 1 W m(-1) K(-1)) compared to the SSR compounds. High power factors combined with low thermal conductivity (leading to ZT values > 0.3) make these phases the best perovskitic candidates as n-type polycrystalline thermoelectric materials operating in air at high temperatures.
The members of the CuMo1-xWxO4 series (0<or=x<0.1) undergo a first-order phase transition at normal pressure, which can be induced by temperature. The two allotropic forms exhibit two distinguishable colors, green for the high-temperature form (alpha) and brownish-red for the low temperature one (gamma), which opens up a new market for user-friendly temperature indicators. From X-ray diffraction and microprobe analyses as from optical properties, the tungsten substitution rate for molybdenum is limited to 12%. Beyond, a third, parasitic wolframite-type phase, CuMo0.6W0.4O6, systematically crystallizes besides the alpha/gammaCuMo0.9W0.1O4 compounds. Within the CuMo1-xWxO4 solid-solution domain, the dependence of the transition temperatures was followed by calorimetry, optical reflectivity, and magnetism. On the basis of these measurements, the transition is characterized for all of the chemical compositions by a hysteresis loop of about 90 K in width with a temperature transition strongly dependent on the tungsten content. Namely, the gamma-->alpha transition can occur between 260 and 360 K, and the alpha-->gamma transition between 175 and 275 K as a function of x. The control of the alpha/gamma transition temperatures with x is related to the larger propensity of tungsten compared to molybdenum, to adopt a tetrahedral environment.
The reactions among Eu2O3, AlN, and Al2O3 with the ratios Eu:Al = 2:1 and 1:2 at 1200 °C for 10 h yielded Eu2AlO3.75N0.1 and EuAl2O4, respectively. The powder X-ray diffraction pattern of the new oxynitride could be indexed as a monoclinic structure with the space group I2 (No. 5) (a = 3.7113(2) Å, b = 3.6894(2) Å, c = 12.3900(8) Å, and β = 90.6860(5)°). This structure was found to be a novel distorted Ruddlesden-Popper type. For EuAl2O4, isostructural with monoclinic SrAl2O4 (space group P21, No. 4), a structural refinement was performed, indicating that the cell parameters were a = 8.44478(11) Å, b = 8.82388(12) Å, c = 5.15643(7) Å, and β = 93.1854(12)°. (151)Eu Mössbauer spectra revealed that the divalent and trivalent Eu ions coexisted in Eu2AlO3.75N0.1, while Eu ions were in the divalent state in EuAl2O4. A photoluminescent mechanism due to 4f(7) ((8)S7/2) ↔ 4f(6)5d(1) of europium in EuAl2O4 was proposed on the basis of the calculated band structure, the band gap obtained from UV-vis diffuse reflectance spectra, and the photoluminescence spectra.
The addition of small amounts of iodine to thermodynamically instable TeCl2 yields amorphous, glassy tellurium(II) halides TeCl2-xIx (0.1 < x < 0.5), which were prepared by rapid quenching of melts with the respective compositions. At ambient temperature, these glassy solids are sufficiently stable to be handled and investigated by analytical methods. High-energy X-ray diffraction and reverse Monte Carlo simulations of two compositions TeCl2-xIx, x = 0.1 and 0.5, show that these glasses are made up of structural fragments that are present in both tellurium tetrahalides and in low-valent tellurium subhalides. In both glasses, the Te-Te bonding shows narrow coordination distribution with a mean total coordination number for the Te atoms of 4.1 +/- 1.3 and a mean Te-Te coordination number of 0.7 +/- 0.7. Accordingly, the mean Cl-Te coordination number is 1.7 +/- 0.8 and the mean I-Te coordination number is 1.6 +/- 0.7. The medium-range order increases with increasing iodine content.
Members of the solid solution series of CeRu1-xNixAl can be obtained directly by arc melting of the elements. The presented compounds with 0.1 ≤ x ≤ 0.85 crystallize in the orthorhombic space group Pnma (No. 62) in the LaNiAl structure type, while for 0.9 ≤ x ≤ 1, the hexagonal ZrNiAl-type structure is found. The orthorhombic members exhibit an anomaly in the trend of the lattice parameters as well as an interesting behavior of the magnetic susceptibility, suggesting that the cerium cations exhibit no local moment. Besides the mixed-valent nature of the cerium cations, valence fluctuations along with a change in the cerium oxidation state depending on the nickel content have been found. The oxidation state has been determined from the magnetic data and additionally by XANES. Density functional theory calculations have identified the shortest Ce-Ru interaction as decisive for the stability of the orthorhombic solid solution.
Band structure engineering is an efficient technique to develop desired semiconductor photocatalysts, which was usually carried out through isovalent or aliovalent ionic substitutions. Starting from a UV-activated catalyst ZnGa2S4, we successfully exploited good visible light photocatalysts for H2 evolution by In(3+)-to-Ga(3+) and (Cu(+)/Ga(3+))-to-Zn(2+) substitutions. First, the bandgap of ZnGa2-xInxS4 (0 ≤ x ≤ 0.4) decreased from 3.36 to 3.04 eV by lowering the conduction band position. Second, Zn1-2y(CuGa)yGa1.7In0.3S4 (y = 0.1, 0.15, 0.2) provided a further and significant red-shift of the photon absorption to ∼500 nm by raising the valence band maximum and barely losing the overpotential to water reduction. Zn0.7Cu0.15Ga1.85In0.3S4 possessed the highest H2 evolution rate under pure visible light irradiation using S(2-) and SO3(2-) as sacrificial reagents (386 μmol/h/g for the noble-metal-free sample and 629 μmol/h/g for the one loaded with 0.5 wt % Ru), while the binary hosts ZnGa2S4 and ZnIn2S4 (synthesized using the same procedure) show 0 and 27.9 μmol/h/g, respectively. The optimal apparent quantum yield reached to 7.9% at 500 nm by tuning the composition to Zn0.6Cu0.2Ga1.9In0.3S4 (loaded with 0.5 wt % Ru).
High-pressure studies of (Mg(0.9)Fe(0.1))2SiO4 olivine were performed at ambient temperature using X-ray diffraction, Raman spectroscopy, and Mössbauer spectroscopy. At approximately 40 GPa, a change of compressibility associated with saturation of the anisotropic compression mechanism was detected. This change is interpreted to result from the appearance of Si2O7 dimer defects, as deduced from Raman spectroscopy; the appearance of such defects also accounts for the previously reported pressure-induced amorphization observed for this material upon additional compression. Furthermore, this behavior is followed by a spin crossover of Fe(2+) that occurs over a wide pressure range, as revealed by Mössbauer spectroscopy.
A polycrystalline sample of a new phase in the Sr-Fe-Mn-O system has been prepared by standard solid-state techniques. Characterization at room temperature by X-ray diffraction, high-resolution electron microscopy, Mössbauer spectroscopy and neutron diffraction has led to it being described as a 15-layered, rhombohedral (15R) perovskite [space group R&thremacr;m: a = 5.4489(1) Å, c = 33.8036(7) Å] with a previously unobserved structure. The pseudo close-packed SrO(3) layers have a (cchch)(3) stacking sequence such that the occupation of the interstitial 6-coordinate sites by Mn (or Fe) leads to the formation of Mn(2)O(9) units which are linked to each other either directly by a common vertex, or indirectly via a single, vertex-sharing MnO(6) octahedron. The stoichiometry of the compound was determined to be SrMn(0.915(5))Fe(0.085(5))O(2.979(3)). The face-sharing sites are occupied by 0.957(3)Mn/0.043(3)Fe while the exclusively corner-linked sites show a higher Fe occupation; 0.745(4)Mn/ 0.255(4)Fe. A neutron diffraction experiment carried out at 3 K indicated the presence of long-range magnetic order with the Mn(4+) cations aligned antiferromagnetically with an ordered moment of 2.26(3)&mgr;(B)/Mn(4+). Both the neutron and the susceptibility data are consistent with the Fe cations remaining magnetically disordered to 3 K. The latter data show T(N) = 220 K, and suggest that some spin frustration is present at low temperatures.
New high temperature Aurivillius piezoelectrics Na0.5NdxBi2.5-xNb2O9 (NDBNx, x = 0.1, 0.2, 0.3, and 0.5) with Nd substitution for Bi at the A site were synthesized using a solid state reaction process. Crystal structures of NDBN0.2 and NDBN0.5 were refined with the Rietveld method with powder X-ray diffraction, and they crystallized in the orthorhombic space group A21am [a = 5.48558(8) Å, b = 5.46326(9) Å, c = 24.8940(4) Å, and Z = 4 for NDBN0.2 and a = 5.46872(5) Å, b = 5.46730(5) Å, c = 24.80723(25) Å, and Z = 4 for NDBN0.5], at room temperature. The refinement results and Raman spectroscopy of NDBNx verified that Nd occupied both the A site in the perovskite layers and the cation site in the (Bi2O2)(2+) layers. The Nd substitution induced an enhancement in cation disordering between the A site and the (Bi2O2)(2+) layer and an increase in the degree of the relaxation behavior for NDBNx. The ferroelectric to paraelectric phase transition temperature (Tc) of NDBNx ranged from 735 to 764 °C. Furthermore, the isovalent substitution of Nd for Bi had a great influence on microstructure (grain size and shape), defect concentration (mainly oxygen vacancies), preferred grain orientation (texture), and distortion of the octahedron. The coaction between these effects determined the structure characteristics, phase transition behaviors, and electrical properties of NDBNx.
Construction of the isothermal section in the metal-rich portion (<67 atom % P) of the Mo-Fe-P phase diagram at 800 °C has led to the identification of two new ternary phases: (Mo(1-x)Fe(x))(2)P (x = 0.30-0.82) and (Mo(1-x)Fe(x))(3)P (x = 0.10-0.15). The occurrence of a Co(2)Si-type ternary phase (Mo(1-x)Fe(x))(2)P, which straddles the equiatomic composition MoFeP, is common to other ternary transition-metal phosphide systems. However, the ternary phase (Mo(1-x)Fe(x))(3)P is unusual because it is distinct from the binary phase Mo(3)P, notwithstanding their similar compositions and structures. The relationship has been clarified through single-crystal X-ray diffraction studies on Mo(3)P (α-V(3)S-type, space group I4̅2m, a = 9.7925(11) Å, c = 4.8246(6) Å) and (Mo(0.85)Fe(0.15))(3)P (Ni(3)P-type, space group I4̅, a = 9.6982(8) Å, c = 4.7590(4) Å) at -100 °C. Representation in terms of nets containing fused triangles provides a pathway to transform these closely related structures through twisting. Band structure calculations support the adoption of these structure types and the site preference of Fe atoms. Electrical resistivity measurements on (Mo(0.85)Fe(0.15))(3)P reveal metallic behavior but no superconducting transition.
A poorly conducting ionic material Ce(0.90)Ca(0.10)O(2-δ) was converted to a highly conducting composition by a codoping strategy with Sm(3+) and Gd(3+). A 50% replacement of Ca with either Sm or Gd has increased the conductivity at 550 °C of Ce(0.90)Ca(0.10)O(2-δ) from 0.0040 to 0.0169 S/cm for the Ce(0.90)Ca(0.05)Sm(0.05)O(2-δ) composition and to 0.0184 S/cm for the Ce(0.90)Ca(0.05)Gd(0.05)O(2-δ) composition. The enhancement in the oxide ion conductivity of these codoped samples has been related to the low ionic radii mismatch and the elastic strain. The extended X-ray absorption fine structure measurements on these systems confirmed that Gd, when coupled with Ca, introduced more disorder in the system, leading to lower activation energy and higher conductivity. In addition, a reduction in the Ce-O bond distance and coordination number has also been observed with codoping.
The crystal symmetries of lead hafnate titanate (Pb(HfxTi1-x)O3, PHT) powders with 0.10<or=x<or=0.50 were investigated by high-resolution neutron powder diffraction. Samples with x<or=0.40 were tetragonal (space group P4 mm), while the sample with x=0.50 contained both monoclinic Cm and rhombohedral (modeled using the R3c space group) phases. The role of the B cations (Hf and Ti) and the oxygen octahedra network, in addition to the displacement of Pb ions from their ideal sites, in promoting the phase transformation between the P4 mm and Cm phases was considered. Two types of structural disorder were identified. Diffuse scattering between Bragg reflection peaks was assigned to Pb ion displacement. A second type of structural disorder, revealed by the weak intensities of observed pseudo-cubic 00l reflections with l even and as 00l reflection peak widths significantly broader than the l00 reflection peaks, was observed. This behavior was attributed to disorder in the arrangement of the O-B-O rows parallel to the c axis. For small values of x, this shift was predominantly along the c axis, whereas shifts perpendicular to the c axis increased with increasing x. These features were modeled using an hkl-dependent line-broadening model. The origin of the hkl-dependent line broadening was assigned to the microstrain accompanying a spatial-composition variation. Structural models were tested by computing valence sums and spontaneous polarization values.
In this paper, nest-like Ni1-xPtx (x = 0, 0.03, 0.06, 0.09, and 0.12) hollow spheres of submicrometer sizes have been prepared through a template-replacement route and investigated as catalysts for generating hydrogen from ammonia borane (NH3BH3). Experimental investigations have demonstrated that the obtained Ni1-xPtx alloy hollow spheres exhibit favorable catalytic activities for both the hydrolysis and the thermolysis of NH3BH3. It was found that, in the presence of the Ni0.88Pt0.12 catalyst, the hydrolysis of NH3BH3 causes a quick release of H2, while the thermal decomposition of NH3BH3 occurs at lowered temperatures with increased mass loss. The present results indicate that NH3BH3 along with Ni1-xPtx alloy hollow spheres may find some applications for small-scale on-board hydrogen storage and supply.
The cobalt aluminum silicides Co19Al45Si(10-x) (x = 0.13) and Co5Al14Si2 were synthesized in liquid aluminum and characterized by single-crystal X-ray diffraction. Co19Al45Si(10-x) (x = 0.13) crystallizes in the monoclinic space group C2/c with lattice parameters a = 19.991(2) A, b = 19.143(2) A, c = 12.8137(15) A, beta = 123.583(2) degrees. Co5Al14Si2 adopts the orthorhombic space group Pnma with cell parameters a = 13.8948(19) A, b = 23.039(3) A, c = 7.3397(10) A. Both structures are exceptionally complex with the Co2Si2 rhombus being a common building motif. The coordination environments of cobalt atoms resemble those of the transition metals in typical quasi-crystal approximants. Co5Al14Si2 shows oxidation resistance in air up to 1000 degrees C by forming a dense-packed Al2O3 layer on the surface of the crystal.
The crystal structure of the selective Cs+ ion exchanger D1.6H0.4Ti2SiO7.D2.66H0.34O1.5, known as crystalline silicotitanate or CST, has been determined in both native (D-CST) and in the Cs+-exchanged forms ((Cs, D)-CST) from angle-dispersive and time-of-flight neutron diffraction studies. The final fully exchange Cs+ form transformed from D-CST with unit cell parameters a = 11.0704(3) A c = 11.8917(5) A and space group P42/mbc, to one with a = 7.8902(1) A c = 11.9051(4) A and space group P42/mcm. Rietveld structure refinements of both D-CST and (Cs, D)-CST suggest the transition, and ultimately the selectivity, is driven by changes in the positions of water molecules, in response to the initial introduction of Cs+. The changes in water position appear to disrupt the D-O-O-D dihedral associated with the CST framework in space group P42/mbc which ultimately leads to the structural transition. The new geometric arrangement of the water-deuteroxyl network in (Cs, D)-CST suggests that Dwater-Ddeuteroxyl repulsion forced by Cs+ exchange drives the structural transformation.
The crystal structure of the layered cobalt oxyfluoride Sr(2)CoO(3)F synthesized under high-pressure and high-temperature conditions has been determined from neutron powder diffraction and synchrotron powder diffraction data collected at temperatures ranging from 320 to 3 K. This material adopts the tetragonal space group I4/mmm over the measured temperature range and the crystal structure is analogous to n = 1 Ruddlesden-Popper type layered perovskite. In contrast to related oxyhalide compounds, the present material exhibits the unique coordination environment around the Co metal center: coexistence of square pyramidal coordination around Co and anion disorder between O and F at the apical sites. Magnetic susceptibility and electrical resistivity measurements reveal that Sr(2)CoO(3)F is an antiferromagnetic insulator with the Néel temperature T(N) = 323(2) K. The magnetic structure that has been determined by neutron diffraction adopts a G-type antiferromagnetic order with the propagation vector k = (1/2 1/2 0) with an ordered cobalt moment μ = 3.18(5) μ(B) at 3 K, consistent with the high spin electron configuration for the Co(3+) ions. The antiferromagnetic and electrically insulating states remain robust even against 15%-O substation for F at the apical sites. However, applying pressure exhibits the onset of the metallic state, probably coming from change in the electronic state of square-pyramidal coordinated cobalt.
The crystal structure of τ6-Ti2(Ti0.16Ni0.43Al0.41)3 was solved using XRD and NPD data. τ6-Ti2(Ti,Ni,Al)3 is an isotypic variant of the V2(Co0.57Si0.43)3-type. The structure consists of slabs of the MgZn2-Laves type and slabs of the Zr4Al3-type forming a tetrahedrally close-packed Frank−Kasper structure. Phase relations were determined for a set of isothermal sections at various temperatures. A Schultz−Scheil reaction scheme has been derived which comprises four isothermal reactions all involving the new phase τ6.
(NH4)(0.16)K(1.84)[Ti(2)F(2)(PO(4))(2)(PO(3)OH)] (1) has been synthesized under hydrothermal conditions. The structure, the composition, and the thermal stability of 1 were determined by single-crystal X-ray diffraction; inductively coupled plasma-optical emission spectroscopy; IR spectroscopy; elemental analysis; thermogravimetric analysis-differential scanning calorimetry-mass spectrometry; and solid-state (1)H, (31)P, and (19)F NMR, and the phase purity of the bulk sample was checked by powder X-ray diffraction. Complex 1 is a fluorotitanophosphate having a unique lamella framework with both TiO(5)F octahedra and PO(3)OH tetrahedra on the surface of the layer, which leads to two different hydrogen bondings involving both P-OH and Ti-F groups.
Two new phosphates, Bi(4.25)(PO4)2O(3.375) and Bi(5)(PO(4))(2)O(4.5), have been analyzed by single-crystal X-ray diffraction in the series Bi(4+x)(PO4)2O(3+3x/2) (0.175 < or = x < or = 1). The syntheses of the compositions ranging from x = 0.175 to 0.475 were carried out by the ceramic route. The compositions from x = 0.175 to 0.475 form a solid solution with a structure similar to that of Bi(4.25)(PO4)2O(3.375), while Bi(5)(PO4)2O(4.5) was isolated from a mixture of two phases. Both of the phases form fluorite-related structures but, nevertheless, differ from each other with respect to the arrangement of the bismuth atoms. The uniqueness in the structures is the appearance of isolated PO(4) tetrahedra separated by interleaving [Bi2O2] units. ac impedance studies indicate conductivity on the order of 10(-5) S cm(-1) for Bi(4.25)(PO4)2O(3.375). Crystal data: Bi(4.25)(PO4)2O(3.375), triclinic, space group P (No. 1), with a = 7.047(1) A, b = 9.863(2) A, c = 15.365(4) A, alpha = 77.604(4) degrees, beta = 84.556(4) degrees, gamma = 70.152(4) degrees, V = 980.90(4) A3, and Z = 4; Bi(5)(PO4)2O(4.5), monoclinic, space group C2/c (No. 15), with a = 13.093(1) A, b = 5.707(1) A, c = 15.293(1) A, beta = 98.240(2) degrees, V = 1130.95(4) A(3), and Z = 8.
The new low-dimensional ternary chalcogenide, Nb(1+x)V(1-x)S(5) (x = 0.18), has been prepared and characterized. This compound crystallizes in the monoclinic space group, C2(2h)-P2(1)/m with two formula units in a cell with dimensions a = 9.881(4) A, b = 3.329(1) A, c = 8.775(3) A, and beta = 114.82(3) degrees. The layer is composed of two unique chains of face-sharing Nb-centered bicapped trigonal prisms and edge-sharing M-centered octahedra (M = Nb or V). The electronic structures of the monomeric basic building units, NbS(8) and VS(6), and hypothetical and real one-, two-, and three-dimensional structures making up the compound are examined to understand the nature of inter- and intrachain interactions and orbital overlapping among metals and sulfur atoms. The electronic structure of Nb(1+x)V(1-x)S(5) is essentially given by superimposing those of the individual chains. V d orbitals are found to be crucial for the one-dimensional metallic conductivity along the chain axis.
The new intermetallic phase ZrSn2-xSbx was prepared by arc-melting and annealing at 800 degrees C. It adopts the hexagonal CrSi2-type structure (Pearson symbol hP9, space group P6222 (or P6422), Z = 3, a = 5.51-5.53 A, c = 7.65-7.63 A) and exhibits a significant phase width (0.2 < x < 0.8). In contrast, the parent binary phases adopt different structures: ZrSn2 has the orthorhombic TiSi2-type structure, and ZrSb2 exists as two orthorhombic forms (alpha-ZrSb2, own type; "beta-ZrSb2", PbCl2-type). The structures of ZrSn2, ZrSn2-xSbx, and beta-ZrSb2 are distinguished by the stacking and distortion of nets with composition "ZrQ2" (Q = Sn, Sb). The CrSi2-type and TiSi2-type structures differ only minimally in energy, but interlayer Sb-Sb bonding is important in stabilizing the structure of beta-ZrSb2.
Starting from the parent 10H-Ba(5)Co(5)X(1-x)O(13-δ) (trimeric strings of face-sharing CoO(6) octahedra with terminal CoO(4) tetrahedra, stacking sequence (chhch')(2)) and 6H-Ba(6)Co(6)X(1-x)O(16-δ) (similar with tetrameric strings, stacking sequence chhhch') hexagonal perovskites forms (X = F, Cl; c, h = [BaO(3)] layers ; h' = [BaOX(1-y)] layers), we show here that the Fe incorporation leads to large domains of solid solutions for both X = F and Cl but exclusively stabilizes the 10H-form independently of the synthesis method. In this form, the lowest concentration of h-layers is stabilized by a sensitive metal reduction with increasing the Fe ratio. In a more general context of competition between several hexagonal perovskite polymorphs available for most of the transition metals, this redox change is most probably the key factor driving 1D (face-sharing chains) to 3D (corner-sharing) connectivities. Strikingly, ND data evidence the location of oxygen deficiencies in the tetrahedral (Co/Fe) coordination. This effect is exaggerated at high temperature, while (Co/Fe)O(4-δ) coordinations are completed by the displacement of X(-) anions toward the (Co/Fe) sphere of coordination following a "push-and-pull" mechanism within h'-[BaOX(1-y)] layers. The Fe-incorporation is also accompanied by increasing conduction gaps with predominant 1D variable range hopping. The full series show antiferromagnetic behavior with increasing T(N) as [Fe] increases. For Fe-rich compounds T(N) is estimated about 600 K, as rarely observed for hexagonal perovskite compounds. Finally, magnetic structures of all iron-doped compounds show a site-to-site AFM ordering, different of the magnetic structure of Co-only parent compounds. Here, DFT calculations predict low-spin octahedral Co configurations, but high-spin Fe species in the same sites.
A 1997 Nature paper (Nature 1997, 388, 353-355) and subsequent 1998 J. Am. Chem. Soc. paper (J. Am. Chem. Soc. 1998, 120, 11969-11976) reported that a putative Ru(2)-substituted polyoxoanion, "[WZnRu(2)(III)(H(2)O)(OH)(ZnW(9)O(34))(2)](11-)", (1), is an all inorganic dioxygenase able to incorporate one O(2) into two adamantane CH bonds to yield 2 equiv of 1-adamantanol as the primary product. In a subsequent 2005 Inorg. Chem. publication (Inorg. Chem. 2005, 44, 4175-4188), strong evidence was provided that the putative dioxygenase chemistry is, instead, the result of classic autoxidation catalysis. That research raised the question of whether the reported Ru(2) precatalyst, 1, was pure or even if it contained two Ru atoms, since Ru is known to be difficult to substitute into polyoxoanion structures (Nomiya, K.; Torii, H.; Nomura, K.; Sato, Y. J. Chem. Soc. Dalton Trans. 2001, 1506-1521). After our research group had contact with three other groups who also had difficulties reproducing the reported synthesis and composition of 1, we decided to re-examine 1 in some detail. Herein we provide evidence that the claimed 1 actually appears to be the parent polyoxoanion [WZn(3)(H(2)O)(2)(ZnW(9)O(34))(2)](12-) with small amounts of Ru (</=0.2 atoms) either substituted into the parent complex or present as a small amount of a Ru(n+) impurity, at least in our and two other group's hands. The evidence obtained, on three independent samples prepared from two research groups including ours, includes elemental analysis on the bulk samples, single crystal X-ray diffraction, elemental analysis on single crystals from the same batch used for X-ray diffraction, (183)W NMR, and adamantane oxidation oxygen uptake and product determination studies. Also re-examined herein are the two previously reported crystal structures of 1 that appear to be very similar to the structure of the parent polyoxoanion, [WZn(3)(H(2)O)(2)(ZnW(9)O(34))(2)](12-). Furthermore, we report that trace Ru alone, in the form of [Ru(DMSO)(4)Cl(2)], or that the parent polyoxoanion [WZn(3)(H(2)O)(2)(ZnW(9)O(34))(2)](12-) alone, are capable of producing the same products. More significantly, a simple physical mixture of [WZn(3)(H(2)O)(2)(ZnW(9)O(34))(2)](12-) plus the average 0.13 equiv of Ru found by analysis added as the [Ru(DMSO)(4)Cl(2)] starting material is a ca. 2-fold kinetically more competent catalyst than is "[WZnRu(2)(III)(H(2)O)(OH)(ZnW(9)O(34))(2)](11-)", (1). In short, the evidence is strong that the putative "[WZnRu(2)(III)(H(2)O)(OH)(ZnW(9)O(34))(2)](11-)", (1), which underlies the previously reported all-inorganic dioxygenase catalysis claim, is probably not correct. That does not mean that 1 cannot or even does not exist, but just that (a) no reliable synthesis of it exists if it has actually been made before, and (b) that a simple mixture of the [Ru(DMSO)(4)Cl(2)] plus [WZn(3)(H(2)O)(2)(ZnW(9)O(34))(2)](12-) precursors gives about 2-fold faster catalysis of adamantane hydroxylation that occurs by, the evidence suggests, a radical-chain autoxidation mechanism rather than via the previously claimed, novel all-inorganic-based dioxygenase catalysis.
A new complex (1) of Prussian blue analogue with the composition of K0.2Mn1.4Cr(CN)6 x 6H2O was prepared and characterized structurally as well as magnetically. The crystal structure of complex 1 was determined by X-ray diffraction analysis. The results indicate that complex 1 consists of a 3D cubic lattice similar to those of Mn3[Cr(CN)6]2 x xH2O, Mn3[Co(CN)6]2 x xH2O, Cd3[Cr(CN)6]2 x xH2O, and Cd3[Co(CN)6]2 x xH2O. Magnetic measurements show that complex 1 is a ferrimagnet with T(c) = 66 K. It is interesting to note that the magnetic behavior of complex 1 can be substantially modulated through a dehydration/rehydration treatment. The T(c) value of this ferrimagnet increases to 99 K after dehydration reaching a 23.4% weight loss, and it decreases back to 66 K after the dehydrated sample reabsorbs water molecules.
The (Ba,Sr)FeO(3-δ) system is known for its strong tendency for oxygen and vacancies to order into several forms including fully ordered pseudobrownmillerites, hexagonal perovskites with segregation of the vacancies in particular anionic layers and low deficient (pseudo)cubic compounds (generally δ < 0.27, Fe(3/4+)). We show for the first time, using a simple chemical process, the easy access to a large amount of vacancies (δ ≈ 0.5, Fe(3+)) within the room-temperature stable tetragonal (pseudocubic) Sr(0.8)Ba(0.2)FeF(~0.1)(O,F)(~2.5.) The drastic effect of the incorporation of a minor amount of fluoride passes through the repartition of local O/F/□ constraints shifting the tolerance factor into the pseudocubic range for highly deficient compounds. It is stable up to 670 K, where an irreversible reoxidation process occurs, leading to the cubic-form. The comparison with the cubic oxide Sr(0.8)Ba(0.2)FeO(~2.7) shows the increase of the resistivity (3D-VRH model) by two decades due to the almost single valent Fe(3+) of the oxofluoride. In addition, the G-type magnetic ordering shows relatively weak moment for Fe(3+) cations (M(Fe) ≈ 2.64(1) μB at room temperature) attributed to incoherent magnetic components expected from local disorder in such anionic-deficient compounds.
Solid solutions BiMn1-xMxO3 with M=Al, Sc, Cr, Fe, and Ga and 0<or=x<or=0.2 were prepared at a high pressure of 6 GPa and 1333-1453 K, and their magnetic, thermal, and structural properties were investigated. The orbital-ordered monoclinic phase of BiMnO3 (phase I) is destroyed by a small percentage of substitution. The M elements can be classified by their ability to destroy phase I in the sequence Ga (x approximately 0.08) approximately Fe (x approximately 0.08)<Cr (x approximately 0.04) approximately Al (x approximately 0.04)<Sc (x approximately 0.02), where phase I is most stable for Ga substitution (up to x approximately 0.08) and less stable for Sc substitution (up to x approximately 0.02). The orbital-disordered high-temperature monoclinic phase of BiMnO3 (phase II) is stabilized with larger x. In all cases, a compositional range was found where phases I and II coexist at room temperature. In phase I, the effect of substitution on the ferromagnetic transition temperature is weak (e.g., TC=102 K for BiMnO3 and TC=99 K for BiMn0.95Ga0.05O3), but there is a drastic effect on the orbital ordering temperature (e.g., TOO=474 K for BiMnO3 and TOO=412 K for BiMn0.95Ga0.05O3). Magnetic susceptibilities of phase I are typical for ferromagnets while, in phase II, ferromagnetic cluster-glass-like behavior is observed. The magnetic transition temperature of phase II (e.g., TC=70 K for BiMn0.8Ga0.2O3) exhibits a sudden drop compared with that of phase I. The effect of substitution on the structural monoclinic-to-orthorhombic transition is different depending on M (e.g., Tstr=768 K for BiMnO3, Tstr=800 K for BiMn0.95Ga0.05O3, and Tstr=738 K for BiMn0.85Cr0.15O3).
A new solid solution Pb(3-x)Bi(2x/3)V(2)O(8) (0.20 < or = x < or = 0.50), stabilizing the high-temperature gamma form of Pb(3)V(2)O(8), has been isolated in the system Pb(3)V(2)O(8)-BiVO(4). The single-crystal structure of the composition x = 0.50 (Pb(2.5)Bi(1/3)V(2)O(8)) was solved using single-crystal X-ray diffraction (XRD) technique. The compound crystallizes in the trigonal crystal system R3m (No. 166) with a palmierite structural type with a = 5.7463(3) A, c = 20.3047(12) A, V = 580.64(5) A(3), and Z = 3. The final R1 value of 0.0406 was achieved for 217 independent reflections during the structure refinement. The variable-temperature powder XRD shows the absence of any phase transition for all of the members of the solid solution in the limit of 398-80 K. The new solid solution has been characterized by neutron powder diffraction, solid-state UV-vis diffuse-reflectance spectra, scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS). Alternating-current impedance studies indicate conductivity on the order of 10(-4) Omega(-1) cm(-1) for Pb(2.5)Bi(1/3)V(2)O(8). The change in color of the samples from brown to yellow at high temperature was explained by XPS studies, which indicate the plausible formation of the ppm level of Bi(2)O(3) at such elevated temperature ranges.
ULM-14 or [FeF(HPO(4))(2),N(2)C(3)H(12),(H(2)O)(x)()] (x approximately 0.20) was synthesized by the hydrothermal method (24 h, 453 K) under autogenous pressure. ULM-14 crystallizes in the orthorhombic system (space group Pmca, No. 57) with cell parameters a = 7.221(1) Å, b = 8.655(1) Å, c = 19.329(2) Å, and Z = 4. Its structure, solved by single-crystal X-ray diffraction, results from isolated single [FeF(HPO(4))(2)](2)(-)(n)() chains of the tancoite type, with diprotonated amines inserted in between. Mössbauer spectrometry clearly evidences the presence of high-spin-state Fe(3+) ions in octahedral coordination and the remaining water molecules. Both magnetic susceptibility and Mössbauer results indicate that ULM-14 behaves as a paramagnet above 2 K, the intrachains interactions being antiferromagnetic.
Mixed-hydride fluorides EuHxF2-x were prepared by the solid-state reaction of EuF2 and EuH2 under hydrogen gas pressure in an autoclave. Eu(II) luminescence is observed for 0.20 ≤ x ≤ 0.67, while pure EuF2 does not show any emission. The energy of the emission depends strongly on the degree of substitution x. For low hydride contents, yellow emission is observed, whereas higher hydride contents lead to red emission. The red shift is attributed to the nephelauxetic effect of the hydride anion. Remarkably, limited concentration quenching is observed in EuHxF2-x (0.20 ≤ x ≤ 0.67). This observation is explained by suppression of long-range energy migration due to disorder in the local environment of Eu(2+) in the mixed H/F crystals. The strong x dependence of the luminescence maxima proves hydride-fluoride substitution to be a valuable tool to tune the emission wavelength of Eu(II)-containing phosphors.
A metal-segregated layered compound, containing square nets of Cu(pyz)(2)(2+) and buckled V(6)O(16)(2)(-) layers, has been synthesized using hydrothermal techniques to have the composition V(6)O(16)Cu(C(4)H(4)N(2))(2) x (H(2)O)(0.22(1)) (C(4)H(4)N(2) = pyrazine, pyz). The Cu(II) square nets are nearly regular and undergo an antiferromagnetic transition at 8 K. In contrast to the plethora of recently synthesized metal-oxide clusters, chains, and networks in the VO(x)/M/L (M = late transition element; L = organonitrogen ligand) system, this compound is a relatively rare example that contains two different metals distributed into distinct layers. An application of charge density matching to form layered structures is postulated.
An original Ruddlesden-Popper phase, La(0.77)Sr(3.23)Co(2.75)C(0.25)O(8.40+δ), was isolated and studied by electron, X-ray, and neutron diffraction. This structure has complex crystal chemistry resulting from a high degree of flexibility in the structure, comprising the disordered introduction of carbonates into a cobalt layer and an important oxygen deficiency with a preferential repartition of vacancies along the layers stacking sequence. The former is necessary for the stabilization of the system, while the latter can be tuned by postsynthetic treatment, yielding in a large variety of cobalt species formal oxidation states ranging from Co(2+)/Co(3+) in the as-made phase to Co(3+)/Co(4+) when annealed under oxygen pressure. The potential richness deriving from this flexibility is illustrated in terms of the magnetotransport properties and includes a resistivity that varies within a range of 5 orders of magnitude after modulation of the oxygen content with the appearance of negative magnetoresistance and ferromagnetic interactions due to Co(3+)/Co(4+) mixed-valence state.
SrFe(0.75)Mo(0.25)O(3-δ) has been recently discovered as an extremely efficient electrode for intermediate temperature solid oxide fuel cells (IT-SOFCs). We have performed structural and magnetic studies to fully characterize this multifunctional material. We have observed by powder neutron diffraction (PND) and transmission electron microscopy (TEM) that its crystal symmetry is better explained with a tetragonal symmetry (I4/mcm space group) than with the previously reported orthorhombic symmetry (Pnma space group). The temperature dependent magnetic properties indicate an exceptionally high magnetic ordering temperature (T(N) ∼ 750 K), well above room temperature. The ordered magnetic structure at low temperature was determined by PND to be an antiferromagnetic coupling of the Fe cations. Mössbauer spectroscopy corroborated the PND results. A detailed study, with X-ray absorption spectroscopy (XAS), in agreement with the Mössbauer results, confirmed the formal oxidation states of the cations to be mixed valence Fe(3+/4+) and Mo(6+).
The distorted wolframite-type oxides CuWO4 and CuMoO4-III have a structure in which CuO4 zigzag chains, made up of cis-edge-sharing CuO6 octahedra, run along the c-direction and hence exhibit low-dimensional magnetic properties. We examined the magnetic structures of these compounds and their isostructural analogue Cu(Mo(0.25)W0.75)O4 on the basis of the spin-orbital interaction energies calculated for their spin dimers. Our study shows that these compounds consist of two-dimensional (2D) magnetic sheets defined by one superexchange (intrachain Cu-O-Cu) and three super-superexchange (interchain Cu-O.O-Cu) paths, the strongly interacting spin units of these 2D magnetic sheets are the two-leg antiferromagnetic (AFM) ladder chains running along the (a + c)-direction, and the spin arrangement between adjacent AFM ladder chains leads to spin frustration. The similarities and differences in the magnetic structures of CuWO4, CuMoO4-III, and Cu(Mo(0.25)W0.75)O4 were discussed by examining how adjacent AFM ladder chains are coupled via the superexchange paths in the 2D magnetic sheets and how adjacent 2D magnetic sheets are coupled via another superexchange paths along the c-direction. Our study reproduces the experimental finding that the magnetic unit cell is doubled along the a-axis in CuWO(4) and along the c-axis in CuMoO4-III and predicts that the magnetic unit cell should be doubled along the a- and b-axes in Cu(Mo(0.25)W0.75)O4. In the understanding of the strength of a super-superexchange interaction, the importance of the geometrical factors controlling the overlap between the tails of magnetic orbitals was pointed out.
Magnetically bistable solid solutions of Prussian blue analogues with chemical formulas of K(α)Ni(1-x)Co(x)[Fe(CN)(6)](β)·nH(2)O (Ni(1-x)Co(x)Fe) and K(α)Co(γ)[Fe(CN)(6)](y)[Cr(CN)(6)](1-y)·nH(2)O (CoFe(y)Cr(1-y)) have been synthesized and studied using mass spectrometry, Mössbauer spectroscopy, X-ray diffraction, temperature-dependent infrared spectroscopy, and dc magnetometry. These compounds provide insight into interfaces between the photomagnetic Co-Fe Prussian blue analogue and the high-T(C) Ni-Cr Prussian blue analogue that exist in high-T(C) photomagnetic heterostructures. This investigation shows that the bistability of Co-Fe is strongly modified by metal substitution, with Ni(1-x)Co(x)Fe stabilizing high-spin cobalt-iron pairs and CoFe(y)Cr(1-y) stabilizing low-spin cobalt-iron pairs, while both types of substitution cause a dramatic decrease in the bistability of the material.
The influence of the nature of alkali metal cations on the structure of the species obtained from the trivacant precursor A-alpha-[SiW(9)O(34)](10-) has been studied. Starting from the potassium salt 1, K(10)A-alpha-[SiW(9)O(34)].24H(2)O, the sandwich-type complex 2, K(10.75)[Co(H(2)O)(6)](0.5)[Co(H(2)O)(4)Cl](0.25)A-alpha-[K(2)(Co(H(2)O)(2))(3)(SiW(9)O(34) )(2)].32H(2)O, has been obtained. The crystal structures of these two compounds consist of two A-alpha-[SiW(9)O(34)](10-) anions linked by a set of potassium (1) or cobalt plus potassium cations (2), and the relative orientation of the two half-anions is the same. Attempts to link two A-alpha-[SiW(9)O(34)](10-) anions by tungsten atoms instead of cobalt failed whatever the alkali metal cation. Moreover, the nondisordered structure of Cs(15)[K(SiW(11)O(39))(2)].39H(2)O is described. Two [SiW(11)O(39)](8-) anions are linked through a potassium cation with a "trans-oid" conformation, and the potassium occupies a cubic coordination site.
Compounds adopting two new structure types containing discrete lanthanide clusters have been found, CsR(R6CoI12)2 (R = Gd or Er) and (CeI)0.26(Ce6MnI9)2. CsEr(Er6CoI12)2 and CsGd(Gd6CoI12)2 were synthesized in reactions of CsI, RI3, CoI2, and R metals (3:19:6:23) heated to 750 degrees C for 500 h followed by slow cooling (0.1 degrees C/min). The X-ray crystal structure of CsEr(Er6CoI12)2 was solved in the Pa3 space group with a = 18.063(2) A at 250 K (Z = 4, R1 [I > 2sigma(I)] = 0.0459). (CeI)0.26(Ce6MnI9) was synthesized by combining KI, CeI3, MnI2, and Ce metal and heating to 850 degrees C for 500 h. The single-crystal X-ray structure for (CeI)0.26(Ce6MnI9)2 was solved in the trigonal, P3 (147) space group with lattice parameters of a = 11.695(1) A and c = 10.8591(2) A (Z = 2, R1 [I > 2sigma(I)] = 0.0895). Elemental analyses (X-ray photoelectron spectroscopy (XPS) and atomic absorption spectroscopy (AAS)) were performed and show the absence of potassium in the structure. A disorder model was refined for the atoms in the large cavity. The magnetic susceptibility data for CsGd(Gd6CoI12)2 is consistent with strong intracluster ferromagnetic coupling, but intercluster antiferromagnetic coupling suppresses the susceptibility below 70 K.
The title compound was detected and characterized during a systematic study of the Al-rich part of the Co-Al-Si system. The crystal structure was established via single-crystal X-ray diffraction. It represents a new type of structure of intermetallic compounds (Pearson symbol mC26, space group C2/m). The homogeneity range of the phase Co4Al(7+x)Si(2-x) (0.27(3) < or = x < or = 1.05(2)) and equilibria with neighboring phases were studied by electron probe microanalysis (EPMA) and X-ray powder diffraction. The lattice parameters of the compound were found to vary between Al-poor and Al-rich composition (a = 11.949(1)-12.042(1) A, b = 3.9986(4)-4.0186(4) A, c = 7.6596(8)-7.6637(9) A, and beta = 106.581(7)-106.140(7) degrees). A partial disorder caused by the Al/Si substitution in one of the five main group element positions was found, and different ordering models yielding different Al/Si occupation motifs and different distributions of interatomic distances are discussed in detail. Chemical bonding analysis with the electron localization function (ELF) reveals a covalently bonded Al/Si network and rather ionic interactions between Co and the network.
Top-cited authors
Constantinos C. Stoumpos
  • University of Crete
Ku Kalyanasundaram
  • École Polytechnique Fédérale de Lausanne
Nefeli anna Papageorgiou
  • KAT Attica General Hospital
Wolfgang Wernsdorfer
  • Karlsruhe Institute of Technology
Eugenio Coronado
  • University of Valencia