Theresa Block

Unusual Mixed Valence of Eu in Two Materials—EuSr2Bi2S4F4 and Eu2SrBi2S4F4: Mössbauer and X-ray Photoemission Spectroscopy Investigations

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 Mössbauer 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 T, we infer that the valence of Eu-atoms in Eu2SrBi2S4F4 at the 2a-sites exhibits a shift toward 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 semimetallic nature for both compounds.

LiGe(SiMe3)3: A New Substituent for the Synthesis of Metalloid Tin Clusters from Metastable Sn(I) Halide Solutions

The most fruitful synthetic route to metalloid tin clusters applies the disproportionation reaction of metastable Sn(I) halide solutions, whereby Si(SiMe3)3 is mostly used as the stabilizing substituent. Here, we describe the synthesis and application of the slightly modified substituent Ge(SiMe3)3, which can be used for the synthesis of metalloid tin clusters to give the neutral cluster Sn10[Ge(SiMe3)3]6 as well as the charged clusters {Sn10[Ge(SiMe3)3]5}− and {Sn10[Ge(SiMe3)3]4}2−. The obtained metalloid clusters are structurally similar to their Si(SiMe3)3 derivatives. However, differences with respect to the stability in solution are observed. Additionally, a different electronic situation for the tin atoms is realized as shown by 119mSn Mössbauer spectroscopy, giving further insight into the different kinds of tin atoms within the metalloid cluster {Sn10[Ge(SiMe3)3]4}2−. The synthesis of diverse derivatives gives the opportunity to check the influence of the substituent for further investigations of metalloid tin cluster compounds.

Abrupt Europium Valence Change in Eu2Pt6Al15 around 45 K

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)0 s0 (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 change from Eu2+ at higher temperatures (>55 K) to Eu3+ at low temperatures. This valence change was proven by temperature dependent 151Eu Mössbauer spectroscopic investigations. Isostructural Eu2Pt6Ga15 was prepared in comparison, and it shows divalent Eu atoms down to 2.5 K along with antiferromagnetic ordering at TN = 13.1(1) K.

Ternary Mixed-Valence Organotin Copper Selenide Clusters

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 Mössbauer spectroscopy, DFT calculations as well as optical absorption experiments.

EuAu3Al2: Crystal and Electronic Structures and Spectroscopic, Magnetic, and Magnetocaloric Properties

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+).

The stannides REIr2Sn4 (RE=La, Ce, Pr, Nd, Sm)

Abstract 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 F2 values, 44 variables for LaIr2Sn4, a=1840.08(2), b=448.24(4), c=719.6(1) pm, wR2=0.0215, 1265 F2 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 F2 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 RE1+xIr2Sn4−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 (TN=3.3 K) and SmIr2Sn4 (TN=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.

Rare earth-copper-magnesium intermetallics: crystal structure of CeCuMg, magnetocaloric effect of GdCuMg and physical properties of the Laves phases RECu4Mg (RE=Sm, Gd, Tb, Tm)

Abstract The intermetallic magnesium compounds CeCuMg and GdCuMg as well as the ternary Laves phases RECu4Mg (RE=Sm, Gd–Tm) were synthesized from the elements by different annealing sequences in high-frequency and muffle furnaces using niobium ampoules as crucibles. All samples were characterized through the lattice parameters using X-ray powder diffraction (Guinier technique). Two structures were refined from single-crystal X-ray diffractometer data: a=764.75(6), c=414.25(4) pm, space group P6̅2m, wR2=0.0389, 338 F2 values, 15 parameters for CeCuMg (ZrNiAl type) and a=723.18(2) pm, space group F4̅3m, wR2=0.0818, 91 F2 values, eight parameters for Gd1.06(3)Cu4Mg0.94(3) (MgCu4Sn type). The Laves phase shows a small homogeneity range (Gd/Mg mixing). An investigation of the magnetocaloric effect (MCE) of ferromagnetic GdCuMg (ZrNiAl type; TC=82 K) revealed a magnetic entropy change of ΔSM=6.5 J kg−1 K−1 and a relative cooling power of RCP=260 J kg−1 for a field change from 0 to 70 kOe, classifying GdCuMg as a moderate magnetocaloric material for the T=80 K region. Of the Laves phases RECu4Mg, SmCu4Mg shows van-Vleck paramagnetism above a Néel temperature of 10.8(5) K, whereas GdCu4Mg and TbCu4Mg undergo antiferromagnetic phase transitions at about 48 and 30 K, respectively. TmCu4Mg shows Curie-Weiss behavior in the entire temperature range. The electrical resistivity of SmCu4Mg and the specific heat capacity of GdCu4Mg were measured for further characterization.

Rare earth-rich cadmium compounds RE10TCd3 (RE=Y, Tb, Dy, Ho, Er, Tm, Lu; T=Rh, Pd, Ir, Pt) with an ordered Co2Al5-type structure

Abstract Eighteen new rare earth-rich intermetallic phases RE10TCd3 (RE=Y, Tb, Dy, Ho, Er, Tm, Lu; T=Rh, Pd, Ir, Pt) were obtained by induction melting of the elements in sealed niobium ampoules followed by annealing in muffle furnaces. All samples were characterized by X-ray powder diffraction. The structures of four representatives were refined from single-crystal X-ray diffractometer data: ordered Co2Al5 type, P63/mmc, a=951.2(1), c=962.9(2) pm, wR=0.0460, 595 F2 values, 20 parameters for Er10RhCd3; a=945.17(4), c=943.33(4), wR=0.0395, 582 F2 values, 21 parameters for Lu9.89PdCd3.11; a=964.16(6), c=974.93(6) pm, wR=0.0463, 614 F2 values, 21 parameters for Y10Ir1.09Cd2.91; a=955.33(3), c=974.56(3) pm, wR=0.0508, 607 F2 values, 22 refined parameters for Dy9.92IrCd3.08. Refinements of the occupancy parameters revealed small homogeneity ranges resulting from RE/Cd, respectively T/Cd mixing. The basic building units of the RE10TCd3 phases are transition metal-centered RE6 trigonal prisms (TP) that are condensed with double-pairs of empty RE6 octahedra via common triangular faces. A second type of rods is formed by slightly distorted RE3@Cd6RE6 icosahedra which are condensed via Cd3 triangular faces. The shortest interatomic distances occur for RE–T, compatible with strong covalent bonding interactions. Temperature dependent magnetic susceptibility measurements were performed for RE10RhCd3 (RE=Dy–Tm, Lu), RE10IrCd3 (RE=Er, Tm, Lu) and RE10PtCd3 (RE=Y, Lu). While Y10PtCd3 and Lu10TCd3 (T=Rh, Ir, Pt) show Pauli paramagnetic behavior, the compounds containing paramagnetic rare earth elements show Curie-Weiss behavior (the experimental magnetic moments indicate stable trivalent RE3+) and magnetic ordering at low temperatures: TC=80.5 K for Dy10RhCd3 and Neél temperatures of 42.1, 23.3, 12.6, 5.9, 10.0 K for Ho10RhCd3, Er10RhCd3, Er10IrCd3, Tm10RhCd3, Tm10IrCd3, respectively.

Synthesis of a Cyclic Co2Sn2 Cluster Using a Co– Synthon

[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.

Valence State of Eu and Superconductivity in Se-Substituted EuSr2Bi2S4F4 and Eu2SrBi2S4F4

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 Mössbauer 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.