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Novel ground states might be realized in honeycomb lattices with strong spin-orbit coupling. Here we study the electronic structure of α-RuCl_{3}, in which the Ru ions are in a d^{5} configuration and form a honeycomb lattice, by angle-resolved photoemission, x-ray photoemission, and electron energy loss spectroscopy supported by density functional theory and multiplet calculations. We find that α-RuCl_{3} is a Mott insulator with significant spin-orbit coupling, whose low energy electronic structure is naturally mapped onto J_{eff} states. This makes α-RuCl_{3} a promising candidate for the realization of Kitaev physics. Relevant electronic parameters such as the Hubbard energy U, the crystal field splitting 10 Dq, and the charge transfer energy Δ are evaluated.

Polycrystalline Cu3-xP was successfully synthesized in different ionic liquids comprising imidazolium and phosphonium cations. The reaction of elemental copper and red phosphorus in trihexyltetradecylphosphonium chloride at 200 °C led to single-phase Cu3-xP (x = 0.05) within 24 h with a quantitative yield (99%). Liquid-state nuclear magnetic resonance spectroscopy of the ionic liquids revealed degeneration of the imidazolium cations under the synthesis conditions, while phosphonium cations remain stable. The solid products were characterized with X-ray powder diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, solid-state nuclear magnetic resonance spectroscopy, and elemental analysis. A reinvestigation of the electronic transport properties of Cu2.95(4)P showed metallic behavior for the bulk material. The formation of CuP2 during the synthesis of phosphorus-rich Cu3-xP (x ≥ 0.1) was observed.

Pd3Bi2S2 and Pd3Bi2Se2 have been successfully prepared in the form of nanoparticles with diameters of ∼50 nm by microwave-assisted modified polyol synthesis at low temperatures. The composition and morphology of the samples have been studied by means of powder X-ray diffraction as well as electron microscopy methods, including X-ray intensity mapping on the nanoscale. Superconducting properties of the as-prepared samples have been characterized by electrical resistivity measurements down to low temperatures (∼0.2 K). Deviations from the bulk metallic behavior originating from the submicrometer nature of the samples were registered for both phases. A significant critical-field enhancement up to 1.4 T, i.e., 4 times higher than the value of the bulk material, has been revealed for Pd3Bi2Se2. At the same time, the critical temperature is suppressed to 0.7 K from the bulk value of ∼1 K. A superconducting transition at 0.4 K has been observed in nanocrystalline Pd3Bi2S2. Here, a zero-temperature upper critical field of ∼0.5 T has been estimated. Further, spark plasma-sintered Pd3Bi2S2 and Pd3Bi2Se2 samples have been investigated. Their superconducting properties are found to lie between those of the bulk and nanosized samples.

Room-temperature precipitation from aqueous solutions yields the hitherto unknown metastable stoichiometric iron selenide (ms-FeSe) with tetragonal anti-PbO type structure. Samples with improved crystallinity are obtained by diffusion-controlled precipitation or hydrothermal recrystallization. The relations of ms-FeSe to superconducting β-FeSe(1-x) and other neighbor phases of the iron-selenium system are established by high-temperature X-ray diffraction, DSC/TG/MS (differential scanning calorimetry/thermogravimetry/mass spectroscopy), (57)Fe Mössbauer spectroscopy, magnetization measurements, and transmission electron microscopy. Above 300 °C, ms-FeSe decomposes irreversibly to β-FeSe(1-x) and Fe(7)Se(8). The structural parameters of ms-FeSe (P4/nmm, a = 377.90(1) pm, c = 551.11(3) pm, Z = 2), obtained by Rietveld refinement, differ significantly from literature data for β-FeSe(1-x). The Mössbauer spectrum rules out interstitial iron atoms or additional phases. Magnetization data suggest canted antiferromagnetism below T(N) = 50 K. Stoichiometric non-superconducting ms-FeSe can be regarded as the true "parent" compound for the "11" iron-chalcogenide superconductors and may serve as starting point for new chemical modifications.

The influence of external pressure on the electrical transport and magnetic properties of EuCu(2)As(2), crystallizing in a ThCr(2)Si(2)-type structure, is reported. The system is known to be an antiferromagnet below T(N) ≈ 15 K in the absence of external magnetic fields. We find that there is a gradual reduction of T(N) with the application of a magnetic field with an extrapolated value of the critical field of around 18 kOe which can drive T(N) to zero. Electrical resistivity under pressure (<11 GPa) reveals that the magnetic ordering temperature is pushed up dramatically to higher temperatures which is quite interesting if compared with the behavior in isostructural FeAs-based systems containing Eu. Above 7 GPa, the pressure-induced state appears to be ferromagnetic. The results thus reveal interesting changes in the magnetic ordering behavior of this compound with increasing pressure and magnetic fields.

The crystal structure of the title diprotonated diacetyl-triethyl-ene-tetra-mine (DAT) perchorate salt, C(10)H(24)N(4)O(2) (2+)·2ClO(4) (-), can be described as a three-dimensional assembly of alternating layers consisting of diprotonated diacetyl-triethyl-ene-tetra-mine (H(2)DAT)(2+) strands along [100] and the anionic species ClO(4) (-). The (H(2)DAT)(2+) cations in the strands are connected via N-H⋯O hydrogen bonding between the acetyl groups and the amine groups of neighbouring (H(2)DAT)(2+) cations. Layers of (H(2)DAT)(2+) strands and perchlorate anions are connected by a network of hydrogen bonds between the NH and NH(2) groups and the O atoms of the perchlorate anion. The asymmetric unit consits of one perchlorate anion in a general position, as well as of one cation that is located on a center of inversion.

Dark red crystals of Y₈S(14.8), Tb₈S(14.8), Dy₈S(14.9), and Ho₈S(14.9) have been obtained following different reaction routes. The isostructural title compounds adopt the Gd₈Se₁₅ type, a 24-fold superstructure of the ZrSSi-type and can be described in space group A112 (non standard setting of C121, no. 5) with lattice parameter of a = 11.505(1) Å, b = 15.385(1) Å, c = 15.726(1) Å, and γ = 90.21(2)° for Y₈S(15-x); a = 11.660(1) Å, b = 15.468(2) Å, c = 15.844(2) Å, and γ = 90.19(2)° for Tb₈S(15-x); a = 11.584(1) Å, b = 15.340(2) Å, c = 15.789(2) Å, and γ = 90.34(2)° for Dy₈S(15-x); and a = 11.538(1) Å, b = 15.288(2) Å, c = 15.740(2) Å, and γ = 90.23(1)° for Ho₈S(15-x), respectively. The structure consists of an alternating stacking of puckered [RES] (RE, rare-earth metals) double slabs and planar sulfur layers along [001]. The planar sulfur layers have a complex arrangement of S₂²⁻ dinuclear dianions, isolated S²⁻ ions, and vacancies. All compounds contain trivalent rare-earth metal ions, for Tb₈S(15-x) and Dy₈S(15-x) antiferromagnetic order was found at T(N) = 5.4(2) K and 3.8(1) K, respectively. Short wavelength cutoff optical band gaps of 1.6 to 1.7 eV were determined.

Boron is one of the trace elements in the human body which plays an important role in bone growth. Porous mesopore bioactive glass (MBG) scaffolds are proposed as potential bone regeneration materials due to their excellent bioactivity and drug-delivery ability. The aims of the present study were to develop boron-containing MBG (B-MBG) scaffolds by sol-gel method and to evaluate the effect of boron on the physiochemistry of B-MBG scaffolds and the response of osteoblasts to these scaffolds. Furthermore, the effect of dexamethasone (DEX) delivery in B-MBG scaffold system was investigated on the proliferation, differentiation and bone-related gene expression of osteoblasts. The composition, microstructure and mesopore properties (specific surface area, nano-pore volume and nano-pore distribution) of B-MBG scaffolds have been characterized. The effect of boron contents and large-pore porosity on the loading and release of DEX in B-MBG scaffolds were also investigated. The results have shown that the incorporation of boron into MBG scaffolds slightly decreases the specific surface area and pore volume, but maintains well-ordered mesopore structure and high surface area and nano-pore volume compared to non-mesopore bioactive glass. Boron contents in MBG scaffolds did not influence the nano-pore size distribution or the loading and release of DEX. B-MBG scaffolds have the ability to maintain a sustained release of DEX in a long-term span. Incorporating boron into MBG glass scaffolds led to a controllable release of boron ions and significantly improved the proliferation and bone-related gene expression (Col I and Runx2) of osteoblasts. Furthermore, the sustained release of DEX from B-MBG scaffolds significantly enhanced alkaline phosphatase (ALP) activity and gene expressions (Col I, Runx2, ALP and BSP) of osteoblasts. These results suggest that boron plays an important role in enhancing osteoblast proliferation in B-MBG scaffold system and DEX-loaded B-MBG scaffolds show great potential as a release system to enhance osteogenic property for bone tissue engineering application., (Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.)

For a biomaterial to be considered suitable for bone repair it should ideally be both bioactive and have a capacity for controllable drug delivery; as such, mesoporous SiO(2) glass has been proposed as a new class of bone regeneration material by virtue of its high drug-loading ability and generally good biocompatibility. It does, however, have less than optimum bioactivity and controllable drug delivery properties. In this study, we incorporated strontium (Sr) into mesoporous SiO(2) in an effort to develop a bioactive mesoporous SrO-SiO(2) (Sr-Si) glass with the capacity to deliver Sr(2+) ions, as well as a drug, at a controlled rate, thereby producing a material better suited for bone repair. The effects of Sr(2+) on the structure, physiochemistry, drug delivery and biological properties of mesoporous Sr-Si glass were investigated. The prepared mesoporous Sr-Si glass was found to have an excellent release profile of bioactive Sr(2+) ions and dexamethasone, and the incorporation of Sr(2+) improved structural properties, such as mesopore size, pore volume and specific surface area, as well as rate of dissolution and protein adsorption. The mesoporous Sr-Si glass had no cytotoxic effects and its release of Sr(2+) and SiO(4)(4-) ions enhanced alkaline phosphatase activity - a marker of osteogenic cell differentiation - in human bone mesenchymal stem cells. Mesoporous Sr-Si glasses can be prepared to porous scaffolds which show a more sustained drug release. This study suggests that incorporating Sr(2+) into mesoporous SiO(2) glass produces a material with a more optimal drug delivery profile coupled with improved bioactivity, making it an excellent material for bone repair applications., (Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

Bis-pyridylimine ligands with different linking elements are capable of forming unique hexanuclear circular Cu(II) meso-helicates; the self-assembly is controlled by coordination of sulfate ions to the metal centres.

The results of magnetization, heat capacity and electrical resistivity (ρ) studies of the compounds RMAs(2) (R = Pr and Sm; M = Ag, Au), crystallizing in an HfCuSi(2)-derived structure, are reported. PrAgAs(2) orders antiferromagnetically at T(N) = 5 K. The Au analog, however, does not exhibit long range magnetic order down to 1.8 K. We infer that this is due to subtle differences in their crystallographic features, particularly noting that both the Sm compounds with identical crystal structures as that of the former order magnetically nearly at the same temperature (about 17 K). It appears that, in PrAgAs(2), SmAgAs(2) and SmAuAs(2), there is an additional magnetic transition at a lower temperature, as though the similarity in the crystal structure results in similarities in magnetism as well. The ρ for PrAgAs(2) and PrAuAs(2) exhibits a negative temperature coefficient in some temperature range in the paramagnetic state. SmAuAs(2) exhibits a magnetic Brillouin-zone gap effect in ρ at T(N), while SmAgAs(2) shows a well-defined broad minimum well above T(N) around 45 K. Thus, these compounds reveal interesting magnetic and transport properties.

GdCuAs2, GdAu(1-delta)As2 and TbAu(1-delta)As2 crystallize as incommensurately modulated variants of the HfCuSi2 type. Structure models have been developed in the monoclinic superspace group P12(1)/m1(alpha0gamma)00 (No. 11.1). The components of the modulation wavevectors q = alphaa* + 0b* + gammac* are alpha = 0.04 (1) and gamma = 0.48 (1) for GdCuAs2, alpha = 0.03 (1) and gamma = 0.48 (1) for GdAu(1-delta)As2 and alpha = 0.02 (1) and gamma = 0.46 (1) for TbAu(1-delta)As2. The predominant effect of the positional modulation is the distortion of a square net of arsenic atoms, which results in planar zigzag chains. Rod groups and layer groups of the respective structure motifs are identified and discussed.

Rare-earth metal coinage-metal diarsenides LnTAs2 (Ln = Y, La, Ce-Lu; T = Cu, Ag, Au) are known to crystallize in structures closely related to the HfCuSi2 type, which comprises a stacking sequence of puckered TAs layers and planar square As nets, separated by the Ln atoms. CeAu(1-delta)As2, with delta = 0.015 (2), shows an incommensurate positional modulation of the arsenic atoms in the planar As nets. Based on X-ray diffraction data on a twinned crystal, a structure model in the monoclinic superspace group P12(1)/m1(alpha0gamma)00 (No. 11.1) with basic unit-cell parameters of a = 5.804 (1), b = 5.814 (1), c = 10.179 (1) A and beta = 90.09 (8) degrees is presented. The components of the modulation wavevector q = alphaa* + 0b* + gammac* are alpha = 0.08 (1) and gamma = 0.39 (1). The structure comprises cis-trans chains and rectangles of As atoms and displays an intricate stacking sequence of the modulated arsenic nets. Rod groups and layer groups of the respective arrangements are identified and the arrangement of different motifs of the modulated As net is discussed.

Single crystals of LaSeTe(2) have been prepared by reaction of the elements in a LiCl/RbCl flux at 970 K for seven days. Satellite reflections observed in diffraction experiments indicate the presence of an incommensurate lattice distortion, which is of the charge-density-wave (CDW) type. The modulated structure has been solved from X-ray data at 173, 293, and 373 K. LaSeTe(2) crystallizes in the 3+1-dimensional orthorhombic superspace group Cmcm(00gamma)s00 (No. 63.2) with lattice parameters of a=4.295(1), b=25.371(4), c=4.306(1) A (173 K), a=4.297(1), b=25.408(4), c=4.309(1) A (293 K), and a=4.309(1), b=25.481(6), c=4.321(1) A (373 K). The modulation vector q=(0, 0, 0.288) does not change over the temperature interval. Electron holographic investigations confirm the existence of the modulation and help to visualize the charge-density wave.

We report an unusual temperature (T) dependent electrical resistivity (rho) behavior in a class of ternary intermetallic compounds of the type RCuAs2 (R=rare earths). For some rare earths (Sm, Gd, Tb, and Dy) with negligible 4f hybridization, there is a pronounced minimum in rho(T) far above respective Néel temperatures (T(N)). However, for the rare earths which are more prone to exhibit such a rho(T) minimum due to 4f-covalent mixing and the Kondo effect, this minimum is depressed. These findings, difficult to explain within the hitherto-known concepts, present an interesting scenario in magnetism.