Field-induced transition of the magnetic ground state from A-type antiferromagnetic to ferromagnetic order in CsCo2Se2

We report on the magnetic properties of CsCo$_2$Se$_2$ with ThCr$_2$Si$_2$ structure, which we have characterized through a series of magnetization and neutron diffraction measurements. We find that CsCo$_2$Se2$_2$ undergoes a phase transition to an antiferromagnetically ordered state with a N\'eel temperature of $T_{\rm N} \approx$ 66 K. The nearest neighbour interactions are ferromagnetic as observed by the positive Curie-Weiss temperature of $\Theta \approx$ 51.0 K. We find that the magnetic structure of CsCo$_2$Se$_2$ consists of ferromagnetic sheets, which are stacked antiferromagnetically along the tetragonal \textit{c}-axis, generally referred to as A-type antiferromagnetic order. The observed magnitude of the ordered magnetic moment at $T$ = 1.5 K is found to be only 0.20(1)$\mu_{\rm Bohr}$/Co. Already in comparably small magnetic fields of $\mu_0 H_{MM}$(5K) $\approx$ 0.3 T, we observe a metamagnetic transition that can be attributed to spin-rearrangements of CsCo$_2$Se$_2$, with the moments fully ferromagnetically saturated in a magnetic field of $\mu_0 H_{\rm FM}$(5K) $\approx$ 6.4 T. We discuss the entire experimentally deduced magnetic phase diagram for CsCo$_2$Se$_2$ with respect to its unconventionally weak magnetic coupling. Our study characterizes CsCo$_2$Se$_2$, which is chemically and electronically posed closely to the $A_xFe_{2-y}Se_2$ superconductors, as a host of versatile magnetic interactions

Low Temperature Precursor Route for Highly Efficient Spherically Shaped LED-Phosphors M2Si5N8:Eu2+ (M = Eu, Sr, Ba)

The highly efficient nitridosilicate phosphors M2Si5N8 (M = Sr, Ba, Eu) for phosphor-converted pc-LEDs were synthesized at low temperatures using a novel precursor route involving metal amides M(NH2)2. These precursors have been synthesized by dissolution of the respective metals in supercritical ammonia at 150°C and 300 bar. The thermal behavior and decomposition process of the amides were investigated with temperature programmed powder X-ray diffractometry and thermoanalytical measurements (DTA/TG). These investigations rendered the amides as suitable intermediates for reaction with silicon diimide (Si(NH)2). Thus, the desired nitridosilicate phosphors were obtained at relatively low temperatures around 1150−1400°C which is approximately 300°C lower compared to common synthetic approaches starting from metals or oxides. The influence of the thermal treatment on the phosphor morphology has been studied extensively. The accessibility of spherical phosphor particles represents another striking feature of this route since it improves light extraction from the crystallites due to decreasing light guiding and decreasing re-absorption inside the phosphor particle. The synthesized luminescent materials M2Si5N8:Eu2+ (M = Sr, Ba) exhibit quantum efficiencies and emission band widths (FWHM 70−90 nm) comparable to standard phosphor powders. Employment of Eu(NH2)2 as dopant reagent for synthesis of Ba2Si5N8:Eu2+ proved favorable for the formation of spherical crystallites compared to doping with Eu metal, halides, or oxide

A potential model investigation of the low-energy antikaon-nucleon interaction and antikaon-nucleus bound states

The parameters of separable coupled channels s-wave potentials for the strong KN interaction are determined from low energy K⁻p scattering data with additional constraints from π⁻p π∑K° production data. The shifts and widths of the Coulomb bound states in kaonic hydrogen are calculated with these potentials and compared with experiment. Optical potentials are constructed from KN t-matrices derived from the separable potentials and these optical potentials are used to calculate kaonic helium and kaonic carbon shifts and widths which are also compared with experiment

Electronic and Optical Properties of Eu²⁺-Activated Narrow-Band Phosphors for Phosphor-Converted Light-Emitting Diode Applications: Insights from a Theoretical Spectroscopy Perspective

In this work, we present a computational protocol that is able to predict the experimental absorption and emission spectral shapes of Eu2+-doped phosphors. The protocol is based on time-dependent density functional theory and operates in conjunction with an excited-state dynamics approach. It is demonstrated that across the study set consisting of representative examples of nitride, oxo-nitride, and oxide Eu2+-doped phosphors, the energy distribution and the band shape of the emission spectrum are related to the nature of the 4f–5d transitions that are probed in the absorption process. Since the 4f orbitals are very nearly nonbonding, the decisive quantity is the covalency of the 5d acceptor orbitals that become populated in the electronically excited state that leads to emission. The stronger the (anti) bonding interaction between the lanthanide and the ligands is in the excited state, the larger will be the excited state distortion. Consequently, the corresponding emission will get broader due to the vibronic progression that is induced by the structural distortion. In addition, the energy separation of the absorption bands that are dominated by states with valence 4f–5d and a metal to ligand charge transfer character defines a measure for the thermal quenching of the studied Eu2+-doped phosphors. Based on this analysis, simple descriptors are identified that show a strong correlation with the energy position and bandwidth of the experimental emission bands without the need for elaborate calculations. Overall, we believe that this study serves as an important reference for designing new Eu2+-doped phosphors with desired photoluminescence properties

Structural and biochemical characterization of a mitochondrial peroxiredoxin from Plasmodium falciparum

Plasmodium falciparum possesses a single mitochondrion with a functional electron transport chain. During respiration, reactive oxygen species are generated that need to be removed to protect the organelle from oxidative damage. In the absence of catalase and glutathione peroxidase, the parasites rely primarily on peroxiredoxin-linked systems for protection. We have analysed the biochemical and structural features of the mitochondrial peroxiredoxin and thioredoxin of P. falciparum. The mitochondrial localization of both proteins was confirmed by expressing green fluorescent protein fusions in parasite erythrocytic stages. Recombinant protein was kinetically characterized using the cytosolic and the mitochondrial thioredoxin (PfTrx1 and PfTrx2 respectively). The peroxiredoxin clearly preferred PfTrx2 to PfTrx1 as a reducing partner, reflected by the K(M) values of 11.6 μM and 130.4 μM respectively. Substitution of the two dyads asparagine-62/tyrosine-63 and phenylalanine-139/alanine-140 residues by aspartate-phenylalaine and valine-serine, respectively, reduced the K(M) for Trx1 but had no effect on the K(M) of Trx2 suggesting some role for these residues in the discrimination between the two substrates. Solution studies suggest that the protein exists primarily in a homodecameric form. The crystal structure of the mitochondrial peroxiredoxin reveals a fold typical of the 2-Cys class peroxiredoxins and a dimeric form with an intermolecular disulphide bridge between Cys67 and Cys187. These results show that the mitochondrial peroxiredoxin of P. falciparum occurs in both dimeric and decameric forms when purified under non-reducing conditions

Ba3Ga3N5 - A Novel Host Lattice for Eu2+ - Doped Luminescent Materials with Unexpected Nitridogallate Substructure

The alkaline earth nitridogallate Ba3Ga3N5 was synthesized from the elements in a sodium flux at 760°C utilizing weld shut tantalum ampules. The crystal structure was solved and refined on the basis of single-crystal X-ray diffraction data. Ba3Ga3N5 (space group C2/c (No. 15), a = 16.801(3), b = 8.3301(2), c = 11.623(2) Å, β = 109.92 (3)°, Z = 8) contains a hitherto unknown structural motif in nitridogallates, namely, infinite strands made up of GaN4 tetrahedra, each sharing two edges and at least one corner with neighboring GaN4 units. There are three Ba2+ sites with coordination numbers six or eight, respectively, and one Ba2+ position exhibiting a low coordination number 4 corresponding to a distorted tetrahedron. Eu2+ - doped samples show red luminescence when excited by UV irradiation at room temperature. Luminescence investigations revealed a maximum emission intensity at 638 nm (FWHM =2123 cm−1). Ba3Ga3N5 is the first nitridogallate for which parity allowed broadband emission due to Eu2+ - doping has been found. The electronic structure of both Ba3Ga3N5 as well as isoelectronic but not isostructural Sr3Ga3N5 was investigated by DFT methods. The calculations revealed a band gap of 1.53 eV for Sr3Ga3N5 and 1.46 eV for Ba3Ga3N5

Synthesis of Alkaline Earth Diazenides MAEN2 (MAE = Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

The alkaline earth diazenides MAEN2 with MAE = Ca, Sr and Ba were synthesized by a novel synthetic approach, namely, a controlled decomposition of the corresponding azides in a multianvil press at highpressure/ high-temperature conditions. The crystal structure of hitherto unknown calcium diazenide (space group I4/mmm (no. 139), a = 3.5747(6) Å, c = 5.9844(9) Å, Z = 2, wRp = 0.078) was solved and refined on the basis of powder X-ray diffraction data as well as that of SrN2 and BaN2. Accordingly, CaN2 is isotypic with SrN2 (space group I4/mmm (no. 139), a = 3.8054(2) Å, c = 6.8961(4) Å, Z = 2, wRp = 0.057) and the corresponding alkaline earth acetylenides (MAEC2) crystallizing in a tetragonally distorted NaCl structure type. In accordance with literature data, BaN2 adopts a more distorted structure in space group C2/c (no. 15) with a = 7.1608(4) Å, b = 4.3776(3) Å, c = 7.2188(4) Å, β = 104.9679(33)°, Z = 4 and wRp = 0.049). The N−N bond lengths of 1.202(4) Å in CaN2 (SrN2 1.239(4) Å, BaN2 1.23(2) Å) correspond well with a double-bonded dinitrogen unit confirming a diazenide ion [N2]2−. Temperature-dependent in situ powder X-ray diffractometry of the three alkaline earth diazenides resulted in formation of the corresponding subnitrides MAE2N (MAE = Ca, Sr, Ba) at higher temperatures. FTIR spectroscopy revealed a band at about 1380 cm−1 assigned to the N−N stretching vibration of the diazenide unit. Electronic structure calculations support the metallic character of alkaline earth diazenides

Li14Ln5[Si11N19O5]O2F2 with Ln = Ce, Nd-Representatives of a Family of Potential Lithium Ion Conductors

The isotypic layered oxonitridosilicates Li14Ln5[Si11N19O5]O2F2 (Ln = Ce, Nd) have been synthesized using Li as fluxing agent and crystallize in the orthorhombic space group Pmmn (Z = 2, Li14Ce5[Si11N19O5]O2F2: a = 17.178(3), b = 7.6500(15), c = 10.116(2) Å, R1 = 0.0409, wR2 = 0.0896; Li14Nd5 Si11N19O5]O2F2: a = 17.126(2), b = 7.6155 15), c = 10.123(2) Å, R1 = 0.0419, wR2 = 0.0929). The silicate layers consist of dreier and sechser rings interconnected via common corners, yielding an unprecedented silicate substructure. A topostructural analysis indicates possible 1D ion migration pathways between five crystallographic independent Li positions. The specific Li-ionic conductivity and its temperature dependence were determined by impedance spectroscopy as well as DC polarization/depolarization measurements. The ionic conductivity is on the order of 5 × 10−5 S/cm at 300°C, while the activation energy is 0.69 eV. Further adjustments of the defect chemistry (e.g., through doping)can make these compounds interesting candidates for novel oxonitridosilicate based ion conductors

Luminescence tuning of MOFs via ligand to metal and metal to metal energy transfer by co-doping of 2∞[Gd2Cl6(bipy)3]*2bipy with europium and terbium

The series of anhydrous lanthanide chlorides LnCl3, Ln=Pr–Tb, and 4,4'-bipyridine (bipy) constitute isotypic MOFs of the formula 2∞[Ln2Cl6(bipy)3]*2bipy. The europium and terbium containing compounds both exhibit luminescence of the referring trivalent lanthanide ions, giving a red luminescence for Eu3+ and a green luminescence for Tb3+ triggered by an efficient antenna effect of the 4,4'-bipyridine linkers. Mixing of different lanthanides in one MOF structure was undertaken to investigate the potential of this MOF system for colour tuning of the luminescence. Based on the gadolinium containing compound, co-doping with different amounts of europium and terbium proves successful and yields solid solutions of the formula 2∞[Gd2-x-yEuxTbyCl6(bipy)3]*2bipy (1–8), 0≤x, y≤0.5. The series of MOFs exhibits the opportunity of tuning the emission colour in-between green and red. Depending on the atomic ratio Gd:Eu:Tb, the yellow region was covered for the first time for an oxygen/carboxylate-free MOF system. In addition to a ligand to metal energy transfer (LMET) from the lowest ligand-centered triplet state of 4,4'-bipyridine, a metal to metal energy transfer (MMET) between 4f-levels from Tb3+ to Eu3+ is as well vital for the emission colour. However, no involvement of Gd3+ in energy transfers is observed rendering it a suitable host lattice ion and connectivity centre for diluting the other two rare earth ions in the solid state. The materials retain their luminescence during activation of the MOFs for microporosity