Eu(O2 C-C≡C-CO2 ): An EuII Containing Anhydrous Coordination Polymer with High Stability and Negative Thermal Expansion.

Anhydrous EuII -acetylenedicarboxylate (EuADC; ADC2- = - O2 C-C≡C-CO2 - ) was synthesized by reaction of EuBr2 with K2 ADC or H2 ADC in degassed water under oxygen-free conditions. EuADC crystallizes in the SrADC type structure (I41 /amd, Z=4) forming a 3D coordination polymer with a diamond-like arrangement of Eu2+ nodes (msw topology including the connecting ADC2- linkers). Deep orange coloured EuADC is stable in air and starts decomposing upon heating in an argon atmosphere only at 440 °C. Measurements of the magnetic susceptibilities (µeff =7.76 µB ) and 151 Eu Mössbauer spectra (δ=-13.25 mm s-1 at 78 K) confirm the existence of Eu2+ cations. Diffuse reflectance spectra indicate a direct optical band gap of Eg =2.64 eV (470 nm), which is in accordance with the orange colour of the material. Surprisingly, EuADC does not show any photoluminescence under irradiation with UV light of different wavelengths. Similar to SrADC, EuADC exhibits a negative thermal volume expansion below room temperature with a volume expansion coefficient αV =-9.4(12)×10-6  K-1 .

The Earlier the Better: Structural Analysis and Separation of Lanthanides with Pyrroloquinoline Quinone.

Lanthanides (Ln) are critical raw materials, however, their mining and purification have a considerable negative environmental impact and sustainable recycling and separation strategies for these elements are needed. In this study, the precipitation and solubility behavior of Ln complexes with pyrroloquinoline quinone (PQQ), the cofactor of recently discovered lanthanide (Ln) dependent methanol dehydrogenase (MDH) enzymes, is presented. In this context, the molecular structure of a biorelevant europium PQQ complex was for the first time elucidated outside a protein environment. The complex crystallizes as an inversion symmetric dimer, Eu2 PQQ2 , with binding of Eu in the biologically relevant pocket of PQQ. LnPQQ and Ln1Ln2PQQ complexes were characterized by using inductively coupled plasma mass spectrometry (ICP-MS), infrared (IR) spectroscopy, 151 Eu-Mössbauer spectroscopy, X-ray total scattering, and extended X-ray absorption fine structure (EXAFS). It is shown that a natural enzymatic cofactor is capable to achieve separation by precipitation of the notoriously similar, and thus difficult to separate, lanthanides to some extent.

Trivalent Antimony as L-, X-, and Z-Type Ligand: The Full Set of Possible Coordination Modes in Pt-Sb Bonds.

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 Mössbauer 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).

[SnI8 {Fe(CO)4 }4 ]2+ : Highly Coordinated Sn+II I8 Subunit with Fragile Carbonyl Clips.

[SnI8 {Fe(CO)4 }4 ][Al2 Cl7 ]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.

Lithiumpyridinyl-Driven Synthesis of High-Purity Zero-Valent Iron Nanoparticles and Their Use in Follow-Up Reactions.

The synthesis of zero-valent iron (Fe(0)) nanoparticles in pyridine using lithium bipyridinyl ([LiBipy]) or lithium pyridinyl ([LiPy]) is presented. FeCl3 is used as the most simple starting material and reduced either in a [LiBipy]-driven two-step approach or in a [LiPy]-driven one-pot synthesis. High-quality nanoparticles are obtained with uniform, spherical shape, and mean diameters of 2.9 ± 0.5 nm ([LiBipy]) or 4.1 ± 0.7 nm ([LiPy]). The as-prepared, high purity Fe(0) nanoparticles are monocrystalline. In addition to particle characterization (high-resolution transmission electron microscopy, scanning transmission electron microscopy, dynamic light scattering), composition and purity are examined in detail based on electron diffraction, X-ray powder diffraction, elemental analysis, infrared spectroscopy, 57 Fe Mössbauer spectroscopy, and magnetic measurements. Due to their small size and high purity, the Fe(0) nanoparticles are highly reactive. They can be used in follow-up reactions to obtain a variety of iron compounds, which is exemplarily shown for the transformation to iron carbide (Fe3 C) nanoparticles, the reaction with sulfur to obtain FeS nanoparticles, or the direct reaction with pentamethylcyclopentadiene to FeCp*2 (Cp*: pentamethylcyclopentadienyl).

An Unusual Valence State: Trivalent Europium in Intermetallic Eu2 Ir3 Al9.

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 Mössbauer spectroscopic investigations unambiguously prove the presence of solely Eu3+ in the bulk material.

From 3D to 2D: Structural, Spectroscopic and Theoretical Investigations of the Dimensionality Reduction in the [PtAl2 ]δ- Polyanions of the Isotypic MPtAl2 Series (M=Ca-Ba, Eu).

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 Mössbauer 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.

Open-Shell 3d Transition Metal Nitridophosphates MII P8 N14 (MII =Fe, Co, Ni) by High-Pressure Metathesis.

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 Mössbauer 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.

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.

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.

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.

Cyclic Distannene or Bis(stannylene) with a Ferrocenyl Backbone: Synthesis, Structure, and Coordination Chemistry.

1,1'-Dilithioferrocene was reacted with 2 equiv of isopropyl (Ar*) or methyl (Ar') substituted terphenyl tin(II) chloride. Reaction product 1, carrying the bulkier terphenyl substituent Ar*, displays a bis(stannylene) structure in the solid state without formation of a tin-tin bond. Temperature-dependent solution 119Sn NMR spectroscopy, however, revealed a dynamic interplay between bis(stannylene) (100 °C) and cyclic distannene (-80 °C). In contrast to 1, the less bulky Ar' substituent results in a cyclic distannene 2. On the basis of temperature-dependent 119Sn NMR spectroscopy the Sn-Sn bond of compound 2 was preserved up to 100 °C. Both compounds were further characterized by solid-state 119Sn NMR spectroscopy as well as 119Sn and 57Fe Mössbauer spectroscopy. 1 reacted as a chelating ligand with nickel and palladium complexes [Ni(cod)2] and [Pd(nbe)3] (nbe = norbornene). In the resulting coordination compounds the nonstabilized stannylene acts as a donor as well as an acceptor ligand and shows a dynamic switch from donor to acceptor behavior in the monopalladium complex.

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.

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.

Fe2 Si5 N8 : Access to Open-Shell Transition-Metal Nitridosilicates.

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, Mössbauer 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.

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.

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+).

Non-innocent cyanido ligands: tetracyanidoferrate(-II) as carbonyl copycat.

While a negative oxidation state occurs rarely for metals in general, this is commonly known for metal carbonyl anions, i.e. carbonyl metalates. Although CO and CN- are isoelectronic, cyanidometalates usually do not exhibit metal centers with negative oxidation states. However, we report on the electron-rich tetrahedral tetracyanidoferrate(-II) anion [Fe(CN)4]6-, which was stabilized in (Sr3N)2[Fe(CN)4] (space group R3c, a = 702.12(2) pm, c = 4155.5(2) pm). Microcrystalline powders were synthesized by a solid-state route, single crystals were obtained from Na metal flux. In comparison to classical cyanidometalates, C-N distances are longer and stretching frequencies are lower as indicated by X-ray diffraction, IR and Raman spectroscopy. Weak C-N, strong Fe-C bonds as well as the anion geometry resemble the isoelectronic tetrahedral carbonyl ferrate [Fe(CO)4]2-. 57Fe Mössbauer spectroscopic measurements reveal a negative isomer shift in agreement with substantially delocalized d electrons due to strong π back-bonding. These results point to a very similar bonding situation of both 18e tetracyanido and tetracarbonyl ferrates including non-innocent redox-active ligands and a d10 closed shell configuration on iron. Hereby, new tetracyanidoferrate(-II) provides a missing link for a more in-depth understanding of the chemical bonding trends of highly-reduced cyanidometalates in the quest for even higher reduced transition metals in this exceptional class of compounds.

Bis(di-tert-butylindenyl)tetrelocenes.

The synthesis and characterization of bis(di-tert-butylindenyl) germanium(II), tin(II) and lead(II) complexes are reported, which includes the first structurally authenticated example of a bis(indenyl)germanocene. The species were studied in detail in solution and in the solid, which includes single crystal X-ray diffraction and NMR spectroscopy, as well as Mössbauer spectroscopy of the tin compound.