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The compounds Pn(pyS)3 (Pn = P, As, Sb, Bi) were synthesized from the respective chloride (Pn = P, As, Sb) or nitrate (Bi), pyridine-2-thiol (pySH) and triethylamine (NEt3) as a supporting base in THF (P, Sb), CHCl3 (As) or methanol (Bi). Sb(pyS)3 was also obtained from the reaction of SbCl3 with LipyS (prepared in situ) in methanol. The compounds Sb(pyS)2Ph and Sb(pyS)Ph2 were prepared in a one-pot reaction starting from SbCl3 and SbPh3 (1:1 ratio). Upon Cl/pyS substitution, the resulting reaction mixture allows for a facile separation of the products in hot hexane. P(pyS)3 and As(pyS)3 crystallize isostructurally to the reported structure of Sb(pyS)3 with κ-S-bound pyS ligands. These crystal structures feature close Pn···Pn contacts which are most pronounced for the arsenic derivative. Bi(pyS)3 adopts a different molecular structure in the solid state, which features two chelating (κ 2-S,N-pyS) ligands and a κ-S-bound ligand. The presence of N→Bi interactions between the nitrogen atom of the κ-S-pyS ligand and the Bi atom of another molecule renders this structure a polymer chain along the crystallographic b axis with Bi⋅⋅⋅Bi van-der-Waals contacts. The structures of this set of Pn(pyS)3 compounds were also studied in solution using 1H NMR spectroscopy, revealing equivalent pyS ligands in discrete Pn(pyS)3 molecules. The molecular structure of Sb(pyS)Ph2 was optimized by quantum chemical methods, and a comparison with the structures reported for the other Sb/pyS/Ph combinations reveals Sb(pyS)2Ph to feature the strongest Sb···N interactions with the κ-S-pyS ligand. The results of 1H NMR spectroscopic investigations of the compounds Sb(pyS) x Ph3–x (x = 3–0) suggest the Ph protons in ortho position to be incorporated into intramolecular C–H···S contacts for x = 2 and 1. Natural localized molecular orbital (NLMO) calculations were employed in order to gain insights into the electronic situations of the Pn atoms and Pn–R bonds (R = S, C), especially for the effects caused by formal substitution of Pn in the compounds Pn(pyS)3 and the ligand patterns in the compounds Sb(pyS) x Ph3–x (x = 3–0). For the latter series of compounds, the electronic situation of the Sb atom was further studied by 121Sb Mössbauer spectroscopy, providing a correlation between the calculated electron density at Sb [ρ(0)] and the experimentally observed isomer shift δ. The missing link between group 15 and group 13 metal compounds of the type M(pyS)3, compound Al(pyS)3, was synthesized in this work. In the solid state (confirmed crystallographically), the mer isomer of this tris-chelate complex with distorted octahedral Al coordination sphere was found. This coordination mode was confirmed for the solution state (CDCl3) by 1H and 13C NMR spectroscopy at T = −40 °C.

Binary antimonides of composition MSb (M = Al, Ga, In), RESb (RE = Sc, Y, La), CdSb, RE4Sb3 (RE = Sc, La), and T5Sb4 (T = Nb, Ta) as well as the pseudobinary solid solutions (La0.25M0.75)4Sb3 (M = ...

The yttrium-rich intermetallic compounds Y14Ni3Cd3 and Y6Co2Zn were obtained by direct reactions of the elements in sealed tantalum tubes in an induction furnace. Both samples were characterized by X-ray powder diffraction and the structures were refined from single-crystal X-ray diffraction data: Lu14Co3In3 type, P42/nmc, a = 960.06(5), c = 2314.9(1) pm, wR2 = 0.0669, 2034 F 2 values, 63 parameters for Y14Ni3.16(2)Cd2.84(2) and Ho6Co2Ga type, Immm, a = 943.08(7), b = 950.08(7), c = 997.64(7) pm, wR2 = 0.0476, 981 F 2 values, 34 parameters for Y6Co2Zn. One cadmium site shows a small degree of Cd/Ni mixing, leading to the composition Y14Ni3.16(2)Cd2.84(2). Although both compounds crystallize with significantly different structure types, they show very similar monomeric building units: (i) transition metal centered trigonal prisms of yttrium, (ii) empty Y6 octahedra and (iii) icosahedral coordination of the cadmium respectively zinc atoms. The condensation patterns of these building units are discussed and for Y14Ni3.16(2)Cd2.84(2), we elaborate a crystal chemical building principle along with the rare earth metal-rich phases RE 15Rh5Cd2 (La15Rh5Cd2 type), RE 23 T 7 X 4 (Pr23Ir7Mg4 type), RE 4 TX (Gd4RhMg type) and RE 10 TX 3/RE 9 TX 4 (ordered Co2Al5 versions). The structures of Y14Ni3Cd3 and Y6Co2Zn show dumbbell formation: 306 pm Cd–Cd in Y14Ni3Cd3 and 224 pm Co1–Co1 and 246 pm Co2–Co2 in Y6Co2Zn.

[SnI8{Fe(CO)4}4][Al2Cl7]2 contains the [SnI8{Fe(CO)4}4]2+ cation with an unprecedented highly coordinated, bicapped SnI8 prism. Given the eightfold coordination with the most voluminous stable halide, it is all the more surprising that this SnI8 arrangement is surrounded only by fragile Fe(CO)4 groups in a clip‐like fashion. Inspite of a predominantly ionic bonding situation in [SnI8{Fe(CO)4}4]2+, the I−⋅⋅⋅I− distances are considerably shortened (down to 371 pm) and significantly less than the van der Waals distance (420 pm). The title compound is characterized by single‐crystal structure analysis, spectroscopic methods (EDXS, FTIR, Raman, UV/Vis, Mössbauer), thermogravimetry, and density functional theory methods., You're clinging! In a clip‐like fashion, Fe(CO)4 groups surround a central SnI8 subunit in [SnI8{Fe(CO)4}4]2+, which has an unprecedentedly high coordination of tin with the most voluminous, stable halide.

The gold-rich intermetallic compounds REAu4Cd2 (RE = La–Nd, Sm) were synthesized from the elements in sealed tantalum ampoules. Their characterization by X-ray powder and single crystal data confirmed the tetragonal YbAl4Mo2 type, space group I4/mmm. The basic building units are Au4 squares (278 pm Au–Au in CeAu4Cd2) and infinite linear cadmium chains (275 pm Cd–Cd in CeAu4Cd2). We exemplarily studied the solid solution CeAu4+ x Cd2− x for x = 0–1 up to CeAu5Cd. Electron diffraction patterns on a CeAu5Cd sample confirm the single crystal data. They give no hint for complete gold-cadmium ordering. Temperature-dependent magnetic susceptibility measurements of CeAu4Cd2, CeAu5Cd, PrAu4Cd2 and NdAu4Cd2 show stable trivalent rare earth ions and give no hint for magnetic ordering above 3 K.

Four new MPtAl2 (M=Ca, Sr, Ba, Eu) compounds, adopting the orthorhombic MgCuAl2 -type structure, have been synthesized from the elements using tantalum ampoules. All compounds are obtained as platelet-shaped crystallites and exhibit an increasing moisture sensitivity with increasing size of the formal M cation. Structural investigations indicate a pronounced elongation of the crystallographic b-axis, which results in a significant distortion of the [PtAl2 ]δ- polyanion. Within the polyanion, layer-like arrangements can be found with bonding Pt-Al interactions within the slab; the increase of the b-axis can be attributed to increasing Al-Al distances and therefore decreasing interactions between the slabs, caused by the differently-sized formal M cations. While the alkaline earth (M=Ca, Sr) representatives exhibit Pauli paramagnetism, BaPtAl2 shows diamagnetic behavior, finally EuPtAl2 is ferromagnetic with TC =54.0(5) K. The effective magnetic moment indicates that the Eu atoms are in a divalent oxidation state, which is confirmed by 151 Eu Mossbauer spectroscopic investigations. Measurements below the Curie-temperature show a full magnetic hyperfine field splitting with Bhf =21.7(1) T. 27 Al and 195 Pt magic-angle spinning NMR spectroscopy corroborates the presence of single crystallographic sites for the Pt and Al atoms. The large 27 Al nuclear electric quadrupolar coupling constants confirm unusually strong electric field gradients, in agreement with the structural distortions and the respective theoretical calculations. X-ray photoelectron spectroscopy has been utilized to investigate the charge transfer within the polyanion. The Pt 4f binding energy decreases with decreasing electronegativity / ionization energy of the alkaline earth elements, suggesting an increasing electron density at the Pt atoms. Theoretical investigations underline the platinide character of the investigated compounds by Bader charge calculations. The analysis of the integrated crystal orbital Hamilton population (ICOHP) values, electron localization function (ELF) and isosurface analyses lead to a consistent structural picture, indicating stable layer-like arrangements of the [PtAl2 ]δ- polyanion.

The rare earth-rich intermetallic compounds RE4OsCd (Gd4RhIn type, RE = La–Nd, Sm, Gd) and RE10OsCd3 (Er10FeCd3 type, RE = Y, Sm, Gd–Tm, Lu) were synthesized by induction melting of the pure elements in sealed niobium ampoules and characterized through their X-ray powder patterns. The structures of Ce4OsCd, Nd4Os0.83Cd1.17, Sm9.87OsCd3.13, and Tm9.89OsCd3.11 were refined from X-ray single crystal diffractometer data. These intermetallics are the first ternary osmium–cadmium compounds. The striking structural feature is an adamantane-like network of osmium-centered trigonal prisms in the RE4OsCd phases with Cd4 tetrahedra (308 pm Cd–Cd in Ce4OsCd) in the cavities. The RE10OsCd3 phases exhibit triangular Cd3 clusters (328 pm Cd–Cd in Sm9.87OsCd3.13) which, together with rare earth atoms, form chains of corner- and face-sharing Cd3RE tetrahedra. Further motifs are Os@RE6 trigonal prisms (TP) that are condensed to empty RE6 octahedra (O), building infinite…TP–O–O… rows in c direction. The two types of rows show the motif of a hexagonal rod packing.

Ternary rare earth metal-rich intermetallic phases containing osmium and magnesium were obtained by induction melting of the elements in sealed niobium ampoules under argon followed by annealing in muffle furnaces. The large rare earth elements form the series of Gd4RhIn-type (F4̅3m) intermetallics RE 4OsMg with RE = La–Nd and Sm, while the smaller rare earth metals gadolinium and terbium form the Y9CoMg4-type (P63/mmc) phases Gd9OsMg4 and Tb9OsMg4. All samples were characterized by X-ray powder diffraction (Guinier technique). The structures of Ce4Os0.973Mg1.027 (a = 1406.54(7) pm, wR2 = 0.0478), Nd4Os0.978Mg1.022 (a = 1402.00(7) pm, wR2 = 0.0463), Sm4Os0.920Mg1.080 (a = 1387.33(5) pm, wR2 = 0.0378) and Gd9OsMg4 (a = 971.01(5), c = 980.43(5) pm, wR2 = 0.0494) were refined from single-crystal X-ray diffractometer data. The three RE 4OsMg phases show small degrees of Os/Mg mixing, as is frequently observed for Rh/In in Gd4RhIn-type intermetallics. The basic building units in both structures are osmium-centered RE 6 trigonal prisms that are condensed with empty RE 6 octahedra. The magnesium atoms in both types build Mg4 tetrahedra. The latter are isolated (312 pm Mg–Mg in Ce4OsMg) and incorporated within the three-dimensional network of prisms and octahedra in the RE 4OsMg phases while one observes rows of corner- and face-sharing tetrahedra in Gd9OsMg4 (305 and 314 pm Mg–Mg). In both structure types direct Os–Mg bonding is not observed.

Phase-pure samples of the antimonides PrPdSb and NdPdSb were prepared by arc-melting pieces of the elements and subsequent annealing. The samples were investigated by powder and single crystal X-ray diffraction: NdPtSb type, space group P63 mc, a = 458.70(5), c = 780.55(6) pm, wR2 = 0.0272, 244 F 2 values, 11 variable parameters for PrPdSb and a = 458.18(4), c = 771.25(6) pm, wR2 = 0.0317, 229 F 2 values, 11 variable parameters for NdPdSb. The palladium and antimony atoms form slightly puckered Pd3Sb3 hexagons which are rotated by 60° in every other layer. The rare earth (RE) atoms are coordinated by two Pd3Sb3 hexagons with the RE–Pd shorter than the RE–Sb contacts. The 121Sb Mössbauer spectra at T = 5 K confirm the antimonide character with isomer shifts of −7.55 (PrPdSb) and −7.47 mm · s−1 (NdPdSb). In agreement with the crystal structures, each spectrum could be fitted with one quadrupole split signal.

Eu2 Ir3 Al9 , synthesized from the elements in tantalum tubes, is one of the rare examples for trivalent europium in the field of intermetallic compounds. The compound crystallizes in the Y2 Co3 Ga9 -type structure (space group Cmcm), with lattice parameters fitting in between the isostructural samarium and gadolinium compounds. In the crystal structure, the Eu atoms form Al3 -triangle-centered honeycomb layers and exhibit a coordination number of 17 in the shape of a fivefold-capped hexagonal prism (Eu@Ir6 Al6 +Al5 ). Magnetic measurements indicate an overall low susceptibility, in line with van Vleck paramagnetism caused by the Eu3+ cations. Fits of the susceptibility yield a coupling constant of λ=290(10) K and an effective magnetic moment of μeff =4.56(1) μB , in line with a slight hybridization of the 7 F0 and 7 F1 state. 151 Eu Mossbauer spectroscopic investigations unambiguously prove the presence of solely Eu3+ in the bulk material.

A series of ternary transition metal gallides around the equiatomic composition have been synthesized from the elements by arc-melting and subsequent annealing. The compounds crystallize with site occupancy variants of the hexagonal Laves phase MgZn2, with the hexagonal ZrBeSi or the orthorhombic TiNiSi type. All samples have been characterized on the basis of their lattice parameters, determined by X-ray powder diffraction (Guinier technique). The structures of NbCr1.58Ga0.42and NbFe1.51Ga0.49(MgZn2type,P63/mmc), NbRhGa (ZrBeSi type,P63/mmc), and ScNiGa, ScPtGa and ScAuGa (TiNiSi type,Pnma) were refined from single crystal X-ray diffractometer data. The ScPtGa and ScAuGa crystals showed trilling formation. Mixed site occupancies were only observed in the Laves phases while all other crystals were well ordered. A striking structural motif of NbRhGa is the formation of niobium chains (264 pm Nb–Nb) along thecaxis. Several gallides were magnetically characterized. They are Pauli paramagnets. The two crystallographically independent iron sites in the Laves phase TaFeGa could be distinguished in the57Fe Mössbauer spectrum. The isomer shifts of 0.06(3) (Fe1) and –0.02(3) (Fe2) mm s−1indicate metallic iron.

The reaction of the antimony(I) compound ArSb (1) (where Ar = C6H3-2,6-(CHNtBu)2) with various dimeric allyl palladium(II) complexes [Pd(η3-allyl)(μ-X)]2 (where allyl = C3H5 or C3H4Me; X = Cl or CF3CO2) in a 1 : 1 stoichiometric ratio gave unique complexes with the μ-ArSb moiety bridging two palladium fragments, i.e. [{Pd(η3-C3H5)Cl}2(μ-ArSb)] (2), [{Pd(η3-C3H4Me)Cl}2(μ-ArSb)] (3) and [{Pd(η3-C3H5)(CF3CO2)}2(μ-ArSb)] (4). Compound 1 serves formally as a 4e donor in 2–4. The treatment of 2 with another equivalent of ArSb led to the formation of the [Pd(η3-C3H5)(Cl)(μ-ArSb)] complex (5), proving that 1 is able to function as a 2e donor in target complexes as well. The structures of 2–5 were described in detail both in solution (NMR and mass spectrometry) and in the solid state (single crystal X-ray diffraction analysis). DFT methods were used to compare bonding in the 1 : 1 (5) and 1 : 2 (2) complexes. Furthermore, a comprehensive 121Sb Mossbauer spectroscopic investigation of complexes 2 and 5 along with parent ArSbCl2 (6) and 1 was performed. For comparison, complexes [Fe(CO)4(ArSb)] (7) and [Mo(CO)5(ArSb)] (8) were also included in this study.

The pnictides Eu14AlAs11 and Eu14AlSb11 were synthesized from the elements in sealed niobium ampoules. They crystallize in the tetragonal crystal system (Eu14AlAs11: a = 1627.6(2), c = 2180.0(4) pm; Eu14AlSb11: a = 1725.6(2), c = 2289.7(7) pm) with space group I41/acd, isostructural to Ca14AlSb11 and can be described as Zintl phases. The Al atoms are surrounded by four pnictogen atoms, forming [AlPn4]9− tetrahedra. Additionally isolated Pn3− anions and linear Pn37− trimers can be found in the crystal structure. The compounds can be described according to (Eu2+)14(AlPn9−)(Pn3−)4(Pn37−). Eu14AlAs11 and Eu14AlSb11 both exhibit an antiferromagnetic transition at TN = 10.5(1) K and 12.5(1) K, respectively. For the antimonide, the magnetic transition has been confirmed by additional heat capacity measurements. Resistivity investigations indicate that Eu14AlSb11 is a semiconductor with a band gap of Eg = 0.28(5) eV close to room temperature. According to the Zintl formalism, the Eu atoms are divalent, which has been confirmed by magnetic susceptibility and additional 151Eu Mossbauer spectroscopic studies. The measurements conducted at 6 K, below the magnetic ordering temperature, show a full hyperfine field splitting with complex spectra underlining the recorded magnetic data. Furthermore, 121Sb Mossbauer spectroscopic studies have been conducted to study the different antimonide entities in the title compounds.

The equiatomic iron-silicides TFeSi as well as the corresponding germanides TFeGe with the electron-poor 4d and 5d transition metals (T=Zr, Nb, Hf, Ta) have been synthesized from the elements by arc-melting. All samples were characterized through their lattice parameters using powder X-ray diffraction (Guinier technique). Four structures were refined from single-crystal X-ray diffractometer data: a=640.16(3), b=393.45(5), c=718.42(6) pm, Pnma, 390 F 2 values, 20 parameters, wR2=0.0294 for ZrFeSi (TiNiSi type), a=719.63(11), b=1119.27(7), c=649.29(7) pm, Ima2, 1103 F 2 values, 54 parameters, wR2=0.0555 for NbFeGe (TiFeSi type), a=655.96(7), c=372.54(4) pm, P6̅2m, 251 F 2 values, 15 parameters, wR2=0.0260 for HfFeGe (ZrNiAl type) and a=624.10(3), b=378.10(6), c=725.25(7) pm, Pnma, 369 F 2 values, 20 parameters, wR2=0.0513 for TaFeGe (TiNiSi type). The common structural motif of the four different structures is the slightly distorted tetrahedral tetrel (tr) coordination of the iron atoms and a trigonal prismatic coordination of iron by T=Zr, Nb, Hf, Ta. Three compounds were characterized as Pauli-paramagnetic by measuring their susceptibility. The measurement of the electrical resistivity of NbFeSi characterises this compound as a good metal. Furthermore, 57Fe Mössbauer spectra of all compounds could be obtained at room temperature, revealing a clear correlation between the structural distortions and the quadrupole splitting parameters.

Single crystals of the high-temperature modification of RhSn4 were obtained from a tin flux (1:20 molar ratio; final annealing at 920 K; dissolution of the tin matrix in 2N HCl). The structure was refined from single-crystal X-ray diffractometer data: I41/acd, a=629.73(5), c=2288.36(18) pm, wR2=0.0382, 447 F 2 values and 14 variables. β-RhSn4 is isotypic with β-IrSn4. The rhodium atoms have slightly distorted square-antiprismatic tin coordination with Rh–Sn distances of 4×273.4 and 4×274.1 pm. The RhSn8 units are condensed via common edges to layers that are staggered with respect to each other and stacked in ABCD sequence. A 119Sn Mössbauer spectroscopic characterization of ß-RhSn4 and the stannides RhSn3 and α-RhSn4 shows the typical isomer shifts for transition metal stannides. Only for α-RhSn4 the three crystallographically independent tin sites could be resolved, a consequence of the different s-electron density. Treatment of α-RhSn4 under high-pressure (up to 10 GPa)/high-temperature (up to T=1370 K) conditions leads to decomposition into Rh1.5Sn, RhSn2 and β-Sn.

3d transition metal nitridophosphates MII P8 N14 (MII =Fe, Co, Ni) were prepared by high-pressure metathesis indicating that this route might give a systematic access to a structurally rich family of M-P-N compounds. Their structures, which are stable in air up to at least 1273 K, were determined through powder X-ray diffraction and consist of highly condensed tetra-layers of PN4 tetrahedra and MN6 octahedra. Magnetic measurements revealed paramagnetic behavior of CoP8 N14 and NiP8 N14 down to low temperatures while, FeP8 N14 exhibits an antiferromagnetic transition at TN =3.5(1) K. Curie-Weiss fits of the paramagnetic regime indicate that the transition metal cations are in a oxidation state +II, which was corroborated by Mossbauer spectroscopy for FeP8 N14 . The ligand field exerted by the nitride ions in CoP8 N14 and NiP8 N14 was determined from UV/Vis/NIR data and is comparable to that of aqua-ligands and oxophosphates.

In the course of our investigations of the coordination chemistry of trivalent antimony (Sb) compounds, we studied heteronuclear complexes formed in reactions of the compounds RSb(pyS)2 (R = pyS, Ph; pyS- = pyridine-2-thiolate) with [Pt(PPh3)4], i.e., complexes [(R)Sb(μ-pyS)2Pt(PPh3)] (R = pyS, 1; R = Ph, 2). The reaction of 1 with o-chloranil proceeds cleanly with elimination of 2,2'-dipyridyl disulfide and formation of the salt [(PPh3)Pt(μ-pyS)2Sb(μ-pyS)2Pt(PPh3)]+[Sb(C6Cl4O2)2]- (3III), which features the cation 3+. The charge-neutral, unsymmetrically substituted compound [(PPh3)Pt(μ-pyS)2Sb(μ-pyS)2Pt(κS-pyS)] (4) can be accessed by the reaction of 3+ with LipyS. The oxidation of 2 with o-chloranil furnishes the complex [(κ-O,O-C6Cl4O2)PhSb(μ-pyS)2Pt(PPh3)] (5). The oxidation of 1 with PhICl2 afforded the paddlewheel-shaped complex [Sb(μ-pyS)4PtCl] (6). Moreover, compound 6 was obtained by the reaction of Sb(pyS)3 with [PtCl(pyS)(PPh3)]. The polarization of Pt-Sb bonds of compounds 1-6 was investigated by natural localized molecular orbital (NLMO) calculations, which suggest X-type ligand character (covalent Pt-Sb bonds) for 1 and 2, whereas the Sb ligand of 6 reflects Z-type character (dative Pt→Sb bonds). In 3+, 4, and 5, high contributions of the reverse, i.e., L-type (dative Pt←Sb bonds), were observed. In conjunction with the results of NLMO analyses, 121Sb Mossbauer spectroscopy proves that complexes 1-6 represent essentially trivalent Sb complexes with either a free lone pair (LP) at the Sb atom (1, 2, and 6) or LP character involved in L-type Pt←Sb coordination (3+, 4, and 5).

[Ar′SnCo]2 (1, Ar′ = C6H3-2,6{C6H3-2,6-iPr2}2), a rare metal–metal bonded cobalt–tin cluster with low-coordinate tin atoms, was prepared by the reaction of [K(thf)0.2][Co(1,5-cod)2] (cod = 1,5-cyclooctadiene) with [Ar′Sn(μ-Cl)]2. This reaction illustrates a promising synthetic strategy to access uncommon metal clusters. The structure of 1 features a rhomboidal Co2Sn2 core with strong metal–metal bonds between tin and cobalt and a weaker tin–tin interaction. Reaction of 1 with white phosphorus afforded [Ar′2Sn2Co2P4] (2), the first molecular cluster compound containing phosphorus, cobalt and tin.

Phase pure Ag2MnSnS4 was synthesized from the elements using standard high-temperature solid-state methods. Its crystal structure was solved from single-crystal X-ray diffraction data collected from a pseudo-merohedrally twinned crystal as well as by Rietveld refinement of X-ray powder diffraction data. Ag2MnSnS4 crystallizes in the monoclinic space group Pc (no. 7) with the unit cell parameters a = 6.651(1), b = 6.943(1), c = 10.536(2) angstrom, beta = 129.15(1)degrees, V = 337.3(1) angstrom(3), and Z = 2. The tetrahedraly compound crystallizes in a superstructure of the wurtzite type and the tetrahedra volumes are in good agreement with the model for diamond-related compounds derived from the wurtzite structure type. The red semiconductor Ag2MnSnS4 has an optical bandgap of E-g = 2.0 eV and is stable up to its peritectic decomposition temperature of approximately 700 degrees C. Ag2MnSnS4 is a Curie-Weiss paramagnet with an experimental magnetic moment of mu(exp) = 5.4(1) mu(B) per manganese atom. Antiferromagnetic ordering is detected at a Neel temperature of T-N = 8.8(1) K. Sn-119 Mo ss bauer spectra at 78 K underline the single tetrahedrally coordinated Sn-IV site (delta = 1.34(1) mm center dot s(-1)). The 6 K spectrum (magnetically ordered state) reveals a small transferred magnetic hyperfine field of 1.02(1) T.

The stannides REIr2Sn4 (RE=La, Ce, Pr, Nd, Sm) were synthesized from the elements by arc melting or by induction melting in sealed niobium containers. They crystallize with the NdRh2Sn4 type structure, space group Pnma. The samples were characterized by powder X-ray diffraction (Guinier technique). Three structures were refined from single-crystal X-ray data: a=1844.5(2), b=450.33(4), c=716.90(6) pm, wR2=0.0323, 1172 F 2 values, 44 variables for LaIr2Sn4, a=1840.08(2), b=448.24(4), c=719.6(1) pm, wR2=0.0215, 1265 F 2 values, 45 variables for Ce1.13Ir2Sn3.87, and a=1880.7(1), b=446.2(1), c=733.0(1) pm, wR2=0.0845, 836 F 2 values, 45 variables for Ce1.68Ir2Sn3.32. The structures consist of three-dimensional [Ir2Sn4] polyanionic networks in which the rare earth atoms fill pentagonal prismatic channels. The striking structural motif concerns the formation of solid solutions RE 1+ x Ir2Sn4− x on the Sn4 sites, which have similar coordination as the RE sites. Temperature dependent magnetic susceptibility measurements revealed diamagnetic behavior for LaIr2Sn4. CeIr2Sn4, PrIr2Sn4 and NdIr2Sn4 show Curie-Weiss paramagnetism while SmIr2Sn4 exhibits typical van Vleck paramagnetism. Antiferromagnetic ground states were observed for CeIr2Sn4 (T N=3.3 K) and SmIr2Sn4 (T N=3.8 K). 119Sn Mössbauer spectra show a close superposition of four sub-spectra which can be distinguished through their isomer shift and the quadrupole splitting parameter.

Eu2Pt6Al15 has been prepared from the elements via arc-melting and subsequent temperature treatment; the structure was refined from single crystal X-ray diffraction data. The compound crystallizes in an orthorhombic (3 + 1)D commensurately modulated structure (Sc2Pt6Al15 type) with space group Cmcm(α,0,0)0s0 (α = 2/3). Full ordering of the Pt and Al atoms within the [Pt6Al15]δ− polyanion was observed. Magnetic measurements revealed an anomaly in the susceptibility data at T = 41.6(1) K, which was also observed as λ-type anomaly in heat capacity measurements (T = 40.7(1) K). Temperature dependent powder X-ray diffraction experiments indicated a drastic shortening of the c axis (−18 pm, −1.1%) around 45 K, while the a axis nearly remains the same (−1 pm, −0.2%). Measurements of the electrical resistivity verified the anomaly, indicating a clear change in the electronic structure of the material. The observed anomalies in the physical measurements can be explained by a temperature driven first order valence ...

Highly condensed nitridosilicates doped with Eu2+ or Ce3+ play an important role in saving energy by converting the blue light of (In,Ga)N-LEDs. Although nitridosilicates are known for great structural variety based on covalent anionic Si-N networks, elemental variety is restricted. Presenting a significant extension of the latter, this work describes a general access to open-shell transition-metal nitridosilicates. As a proof-of-principle, the first iron nitridosilicate, namely Fe2 Si5 N8 , was prepared by exchanging Ca2+ in α-Ca2 Si5 N8 applying a FeCl2 melt (salt metathesis). The title compound was analyzed by powder X-ray diffraction, EDX, ICP-OES, combustion analysis, TG/DSC, Mossbauer spectroscopy and magnetic susceptibility measurements. Furthermore, the structure of α-Ca2 Si5 N8 was determined at 1073 and 1173 K confirming the anionic network of α-Ca2 Si5 N8 providing possible migration pathways for the ion-exchange reaction.

Recently, we reported the synthesis and investigations of EuSr2Bi2S4F4 and Eu2SrBi2S4F4. We have now been able to induce superconductivity in EuSr2Bi2S4F4 by Se substitution at the S site (isovalent substitution) with Tc = 2.9 K in EuSr2Bi2S2Se2F4. The other compound, Eu2SrBi2S4F4, shows a significant enhancement of Tc. In Se-substituted Eu2SrBi2S4–xSexF4, we find Tc = 2.6 K for x = 1.5 and Tc = 2.8 K for x = 2, whereas Tc = 0.4 K in the Se-free sample. In addition to superconductivity, an important effect associated with Se substitution is that it gives rise to remarkable changes in the Eu valence. Our 151Eu Mossbauer and X-ray photoemission spectroscopic measurements show that Se substitution in both of the compounds Eu2SrBi2S4F4 and EuSr2Bi2S4F4 gives rise to an increase in the Eu2+ component in the mixed-valence state of Eu.

The plumbide EuPdPb was synthesized in polycrystalline form by reaction of the elements in a sealed niobium ampoule in a muffle furnace. The structure was refined from single-crystal X-ray diffractometer data: TiNiSi type, Pnma, a=752.4(2), b=476.0(2), c=826.8(2) pm, wR2=0.0485, 704 F 2 values and 20 variables. The europium atoms are coordinated by two tilted and puckered Pd3Pb3 hexagons (280–289 pm Pd–Pb) with pronounced Eu–Pd bonding (312–339 pm). Temperature-dependent magnetic susceptibility measurements show Curie-Weiss behaviour and an experimental magnetic moment of 7.35(1) μB per Eu atom. EuPdPb orders antiferromagnetically at T N=13.8(5) K and shows a metamagnetic transition at a critical field of 15 kOe. 151Eu Mössbauer spectra confirm divalent europium (δ=–10.04(1) mm s−1) and show full magnetic hyperfine field splitting (B hf=21.1(1) T) at 6 K.

Polycrystalline samples of Sr 0.95 Eu 0.05 Ba 8 [BN 2 ] 6 and Eu 0.937 Ba 8 [BN 2 ] 6 were synthesized via conventional solid-state reaction from the binary precursor compounds Sr 3 N 2 , EuN, Ba 3 N 2 and BN at 1000 °C. The structure of Eu 0.937 Ba 8 [BN 2 ] 6 was refined from single crystal X-ray diffractometer data: Eu 0.937 Ba 8 [BN 2 ] 6 type, Fd 3 ¯ m, a = 1594.54(9) pm, w R 2 = 0.0654, 380 F 2 values and 23 variables. The 8 a europium site shows an occupancy of only 93.7(9) % suggesting partial oxidation of europium to fulfil an electron-precise description, i. e. Eu II 0.81 Eu III 0.13 Ba 8 [BN 2 ] 6 . The mixed europium valence was confirmed by magnetic susceptibility measurements (reduced magnetic moment of 7.28 μ B per europium atom) and 151 Eu Mossbauer spectroscopy (Eu II : Eu III = 82: 18). The nitridoborate anions are coordinated by slightly distorted, mono-capped (europium) square prisms formed by the barium atoms. All metal cations are hexa-coordinated by nitrogen atoms. The EPR spectra of Eu x Sr 1-x Ba 8 [BN 2 ] 6 samples (0.001 ≤ x ≤ 0.01) suggest close to cubic local symmetry of the Eu 2+ dopant ions and reveal some highly unusual features: Magnetic hyperfine splitting is only observed with one of the Eu nuclear isotopes, and the coupling constant of 243.6 MHz is extremely large compared to values (90–100 MHz) typically observed in the literature for Eu 2+ doped crystalline materials.

Pyrochlore-type Eu2Ta2(O,N)7+δ phases were prepared by reaction of ammonia with an amorphous europium tantalum oxide precursor. 151Eu Mossbauer and EPR spectroscopy as well as magnetic susceptibility measurements point to the presence of exclusively Eu3+. For phase-pure samples (X-ray powder diffraction), the nitrogen content varies between 1.0 and 1.8 wt %, leading to compositions in the range Eu2Ta2O7.1N0.6 – Eu2Ta2O6.5N1.0. Pyrochlore-type phases are structurally derived from the fluorite type with 1/8 of the anions missing, resulting in an ideal composition A2B2X7. In Eu2Ta2(O,N)7+δ the excess anions partly occupy these vacancies. The prepared phases are colorless with a direct optical bandgap of 4.3 eV and they show the typical Van Vleck paramagnetic behavior known for trivalent Eu atoms.

The ternary antimonide YIrSb was synthesized from the binary precursor YIr and elemental antimony by a diffusion controlled solid-state reaction. Single crystals were obtained by a flux technique with elemental bismuth as an inert solvent. The YIrSb structure (TiNiSi type, space group Pnma) was refined from single-crystal X-ray diffractometer data: a = 711.06(9), b = 447.74(5), c = 784.20(8) pm, wR2 = 0.0455, 535 F2 values, 20 variables. 89Y solid state MAS NMR and 121Sb Mossbauer spectra show single resonance lines in agreement with single-crystal X-ray data. YIrSb is a Pauli paramagnet.

Eu5Al2Sb6 was synthesized from the elements in niobium ampoules. It crystallizes in the orthorhombic crystal system (a = 1027.55(7), b = 1200.28(6), c = 1324.22(7) pm) with space group Pnma (no. 62), isostructural to Sr5Al2Sb6, and can be described as a Zintl phase. The Al atoms are tetrahedrally surrounded by Sb atoms, forming branched strands. Besides Sb3− anions, antimony Sb24− dumbbells can also be found in the crystal structure. Eu5Al2Sb6 [≡(Eu2+)5(Al3+)2(Sb3−)4(Sb24−)] exhibits three magnetic ordering phenomena at T1 = 12.3(1), T2 = 10.6(1) and T3 = 3.0(1) K, obtained by heat capacity measurements. While T3 is of antiferromagnetic nature, T1 and T2 correspond to canted antiferromagnetic transitions. Resistivity investigations indicate that the title compound is a semiconductor, in line with the band structure calculations. Spin exchange parameters, calculated using mapping analysis, confirm that the magnetic phase transition at TN = 3.5(1) is associated with the ordering of Eu1 atoms. The divalent character has been confirmed by 151Eu Mossbauer spectroscopic studies. Measurements conducted at 5 K show a hyperfine field splitting for two of the three Eu sites, underlining the magnetic data. Additionally, 121Sb Mossbauer spectroscopic studies have been conducted on Eu5Al2Sb6 and isostructural Sr5Al2Sb6.

The rare earth borosulfates RE2[B2(SO4)6] with RE = Y, La–Nd, Sm, Eu and Tb–Lu were synthesised under solvothermal conditions starting from the metal chlorides (Pr, Nd, Eu), the metal oxides (Y, La, Ce, Sm, Tb, Dy, Er, Tm, Lu), or the metal powders (Ho, Yb). They crystallize isotypically with Gd2[B2(SO4)6] in space group C2/c (Z = 4, a = 1346.9(3)–1379.24(17) pm, b = 1136.4(3)–1158.87(14) pm, c = 1079.9(3)–1139.54(14) pm, β = 93.369(8)–93.611(4)°). The anionic structure consists of an open-branched vierer single ring {oB, 1r}[B2S2O12(SO3)4]6−, similar to the mineral eakerite (Ca2Al2Sn[Si6O18](OH)2·2H2O) which contains {oB, 1r}[Si4O12(SiO3)2]12− moieties. The fluorescence spectroscopy of the samples with RE = Ce, Eu and Tb features emissions in the deep UV, the red, and the green part of the spectrum and furthermore revealed a weak coordination behaviour of the borosulfate anion. Thermal analysis of Eu2[B2(SO4)6] showed the highest thermal stability observed for borosulfates so far; respective trends within the borosulfate family are discussed. Additionally, the compounds were characterised by magnetic measurements, vibrational and 151Eu Mosbauer spectroscopy.

The intermetallic compound EuAu3Al2 has been prepared by reaction of the elements in tantalum ampules. The structure was refined from single-crystal data, indicating that the title compound crystallizes in the orthorhombic crystal system (a = 1310.36(4), b = 547.87(1), c = 681.26(2) pm) with space group Pnma (wR2 = 0.0266, 1038 F(2) values, 35 parameters) and is isostructural to SrAu3Al2 (LT-SrZn5 type). Full ordering of the gold and aluminum atoms was observed. Theoretical calculations confirm that the title compound can be described as a polar intermetallic phase containing a polyanionic [Au3Al2](δ-) network featuring interconnected strands of edge-sharing [AlAu4] tetrahedra. Magnetic measurements and (151)Eu Mössbauer spectroscopic investigations confirmed the divalent character of the europium atoms. Ferromagnetic ordering below TC = 16.5(1) K was observed. Heat capacity measurements showed a λ-type anomaly at T = 15.7(1) K, in line with the ordering temperature from the susceptibility measurements. The magnetocaloric properties of EuAu3Al2 were determined, and a magnetic entropy of ΔSM = -4.8 J kg(-1) K(-1) for a field change of 0 to 50 kOe was determined. Band structure calculations found that the f-bands of Eu present at the Fermi level of non-spin-polarized calculations are responsible for the ferromagnetic ordering in this phase, whereas COHP chemical bonding coupled with Bader charge analysis confirmed the description of the structure as covalently bonded polyanionic [Au3Al2](δ-) network interacting ionically with Eu(δ+).

Reactions of the organotin selenide chloride clusters [(R1 SnIV )3 Se4 Cl] (A, R1 =CMe2 CH2 C(O)Me) or [(R1 SnIV )4 Se6 ] (B) with [Cu(PPh3 )3-x Clx ] yield cluster compounds with different inorganic, mixed-valence core structures: [Cu4 SnII SnIV6 Se12 ], [Cu2 SnII2 SnIV4 Se8 Cl2 ], [Cu2 SnII SnIV4 Se8 ], [Cu2 SnII2 SnIV2 Se4 Cl4 ], and [Cu2 SnIV2 Se4 ]. Five of the compounds, namely [(CuPPh3 )2 {(R1 SnIV )2 Se4 }] (1), [(CuPPh3 )2 SnII {(R2 SnIV )2 Se4 }2 ] (2), [(CuPPh3 )2 (SnII Cl)2 {(RSnIV )2 Se4 }2 ] (3) [(CuPPh3 )2 (SnII Cu2 ){(R1 SnIV )2 Se4 }3 ] (4), and [Cu(CuPPh3 )(SnII Cu2 ){(R1 SnIV )2 Se4 }3 ] (5) are structurally closely related. They are based on [(CuPPh3 )2 {(RSnIV )2 Se4 }n ] aggregates comprising [(RSnIV )2 Se4 ] and [CuPPh3 ] building units, which are linked by further metal atoms. A sixth compound, [(CuPPh3 )2 (SnII Cl)2 {(R1 SnIV Cl)Se2 }2 ] (6), differs from the others by containing [(RSnIV Cl)Se2 ] units instead, which affects the absorption properties. The compounds were analyzed by single-crystal X-ray diffraction, NMR and 119 Sn Mossbauer spectroscopy, DFT calculations as well as optical absorption experiments.

The intermetallic gold compounds RE 4Mg3Au10 (RE = La, Ce, Pr) and RE 4Cd3Au10 (RE = Y, La–Nd, Sm, Gd–Dy) were obtained from the elements through high-frequency melting in sealed niobium tubes and subsequent annealing in a muffle furnace. The new aurides crystallize with the Ca4In3Au10-type structure. They were characterized through Guinier powder patterns. The structures of Pr4.46Cd2.54Au10 and Tb4.38Cd2.62Au10 were refined from single crystal X-ray diffractometer data: Cmce, a = 1396.73(6), b = 1009.38(3), c = 1019.51(3) pm, wR2 = 0.0423, 1281 F 2 values, 47 variables for Pr4.46Cd2.54Au10 and a = 1362.68(3), b = 995.52(4), c = 1003.79(3) pm, wR2 = 0.0381, 1594 F 2 values, F 2 47 variables for Tb4.38Cd2.62Au10. The 8e sites of both crystals show substantial Cd/Pr respectively Cd/Tb mixing, indicating small homogeneity ranges for all RE 4+x Mg3–x Au10 and RE 4+x Cd3–x Au10 aurides. The gold atoms in these aurides form a pronounced two-dimensional substructure (275–327 pm Au–Au in Pr4.46Cd2.54Au10) which encages the Mg1/Cd1 (coordination number 8) and RE2 (coordination number 11) atoms. These blocks are separated by the Mg2/Cd2 and RE1 atoms with an intergrowth of Mg2/Cd2@Au8 and RE1@Au10 polyhedra. Temperature dependent magnetic susceptibility and specific heat measurements of Tb4Cd3Au10 have shown antiferromagnetic ordering at a Néel temperature of 12(1) K.

The ternary aurides RE 4Mg3Au10 (RE=Y, Nd, Sm, Gd–Dy) and their silver analogues were synthesized by induction melting of the elements in sealed niobium tubes. These intermetallic phases were characterized by powder X-ray diffraction. They crystallize with the Ca4In3Au10-type structure, which, from a geometrical point of view, is a ternary ordered version of Zr7Ni10 with the rare earth and magnesium atoms ordering on the four crystallographically independent zirconium sites. The structures of crystals from three differently prepared gadolinium samples were refined from single-crystal X-ray diffractometer data: Cmca, a=1366.69(3), b=998.07(4), c=1005.54(3) pm, wR2=0.0332, 1234 F 2 values, 46 variables for Gd4.43Mg2.57Au10, a=1378.7(1), b=1005.3(1), c=1011.2(1) pm, wR2=0.0409, 1255 F 2 values, 48 variables for Gd5.50Mg1.50Au10, and a=1350.2(5), b=995.5(1), c=1009.3(1) pm, wR2=0.0478, 1075 F 2 values, 48 variables for Gd5.61Mg1.39Au10. All crystals show substantial Mg/Gd mixing on two sites. The gold atoms form a pronounced two-dimensional substructure with Au–Au distances of 278 to 297 pm in Gd4.43Mg2.57Au10. These gold blocks are condensed via magnesium atoms (278–315 pm Mg–Au). The gadolinium atoms fill larger cavities within the three-dimensional networks. The magnesium vs. gadolinium site preference is a consequence of the different coordination numbers of the cation sites. All phases show homogeneity ranges RE 4+x Mg3–x Ag10 and RE 4+x Mg3–x Au10. The influence of the synthesis conditions is briefly discussed.

The rare earth-rich intermetallic cadmium compounds RE10TCd3 (RE = Y, Tb – Tm, Lu; T = Fe, Co, Ni, Ru, Rh, Pd) were synthesized by induction melting of the elements in sealed niobium ampoules. These cadmium intermetallics crystallize with an ordered variant of the hexagonal Co2Al5 type, space group P63/mmc. The three crystallographically independent rare earth atoms lie on the aluminum sites, while the transition metal and cadmium atoms are ordered on the two cobalt positions. The structures of Y10Co1.103Cd2.897, Y10NiCd3, Y10RuCd3, Y10PdCd3, Er9.92FeCd3.08, and Er9.82NiCd3.18 were refined from single-crystal X-ray diffraction data. Some of the crystals showed small degrees of RE/Cd, respectively T/Cd mixing. The striking structural building units are transition metal centered T@RE6 trigonal prisms (TP) that are condensed to empty RE6 octahedra (O), building infinite …TP–O–O… rows in c direction. The second motifs are slightly flattened RE3@Cd6RE16 icosahedra. The latter are condensed via common triangular faced along the c axis. Each …TP–O–O… row is enrolled by three rows of condensed RE3@Cd6RE16 icosahedra in the motif of a hexagonal rod packing.

We have synthesized two new Eu-based compounds, EuSr2Bi2S4F4 and Eu2SrBi2S4F4 which are derivatives of Eu3Bi2S4F4, an intrinsic superconductor with Tc = 1.5 K. They belong to a tetragonal structure (SG: I4/mmm, Z = 2), similar to the parent compound Eu3Bi2S4F4. Our structural and 151Eu M\"ossbauer spectroscopy studies show that in EuSr2Bi2S4F4, Eu-atoms exclusively occupy the crystallographic 2a-sites. In Eu2SrBi2S4F4, 2a-sites are fully occupied by Eu-atoms and the other half of Eu-atoms and Sr-atoms together fully occupy 4e-sites in a statistical distribution. In both compounds Eu atoms occupying the crystallographic 2a-sites are in a homogeneous mixed valent state ~ 2.6 - 2.7. From our magnetization studies in an applied H = 9 Tesla, we infer that the valence of Eu-atoms in Eu2SrBi2S4F4 at the 2a-sites exhibits a shift towards 2+. Our XPS studies corroborate the occurrence of valence fluctuations of Eu and after Ar-ion sputtering show evidence of enhanced population of Eu2+-states. Resistivity measurements, down to 2 K suggest a semi-metallic nature for both compounds.

The intermetallic compound EuAu3Al2 has been prepared by reaction of the elements in tantalum ampules. The structure was refined from single-crystal data, indicating that the title compound crystallizes in the orthorhombic crystal system (a = 1310.36(4), b = 547.87(1), c = 681.26(2) pm) with space group Pnma (wR2 = 0.0266, 1038 F(2) values, 35 parameters) and is isostructural to SrAu3Al2 (LT-SrZn5 type). Full ordering of the gold and aluminum atoms was observed. Theoretical calculations confirm that the title compound can be described as a polar intermetallic phase containing a polyanionic [Au3Al2](δ-) network featuring interconnected strands of edge-sharing [AlAu4] tetrahedra. Magnetic measurements and (151)Eu Mossbauer spectroscopic investigations confirmed the divalent character of the europium atoms. Ferromagnetic ordering below TC = 16.5(1) K was observed. Heat capacity measurements showed a λ-type anomaly at T = 15.7(1) K, in line with the ordering temperature from the susceptibility measurements. The magnetocaloric properties of EuAu3Al2 were determined, and a magnetic entropy of ΔSM = -4.8 J kg(-1) K(-1) for a field change of 0 to 50 kOe was determined. Band structure calculations found that the f-bands of Eu present at the Fermi level of non-spin-polarized calculations are responsible for the ferromagnetic ordering in this phase, whereas COHP chemical bonding coupled with Bader charge analysis confirmed the description of the structure as covalently bonded polyanionic [Au3Al2](δ-) network interacting ionically with Eu(δ+).

The title compounds are synthesized from the elements (flowing Ar, 1500 K for 2 min, 1300 K for 45 min, and 900 K for 2 h) and characterized by powder XRD.