Oligo-Condensation Reactions of Silanediols with Conservation of Solid-State-Structural Features.

Oligo- and polysiloxanes are usually prepared by condensation reactions in solvents without control of stereochemistry. Here we present a solventless thermal condensation of stable organosilanols. We investigated the condensation reactions of organosilanediols with different organic substituents, having in common at least one aromatic group. The condensation kinetics of the precursors observed by NMR spectroscopy revealed a strong dependence on temperature, time, and substitution pattern at the silicon atom. SEC measurements showed that chain length increases with increasing condensation temperature and time and lower steric demand of the substituents, which also influences the glass transition temperatures (Tg) of the resulting oligo- or polymers. X-ray diffraction studies of the crystalline silanediols and their condensation products revealed a structural correlation between the substituent location in the crystalline precursors and the formed macromolecules induced by the hydrogen bonding pattern. In certain cases, it is possible to carry out topotactic polymerization in the solid-state, which has its origin in the crystal structure.

Searching for Laves Phase Superstructures: Structural and 27Al NMR Spectroscopic Investigations in the Hf-V-Al System.

Laves phases exhibit a plethora of different structures and a multitude of physical properties. Investigations in the ternary system Hf-V-Al led to the discovery of numerous members of the solid solution Hf(V1-xAlx)2, which adopt the hexagonal MgZn2 type (C14) for medium to high amounts of Al (x = 0.2-1) and the cubic MgCu2 type (C15) for small Al amounts (x = 0.05-0.1). While all members exhibit Pauli-paramagnetic behavior due to the absence of localized magnetic moments, the V-rich cubic member Hf(V0.95Al0.05)2 additionally exhibits a superconducting state below TC = 7.6(1) K. All synthesized compounds were characterized by powder X-ray diffraction, and selected samples were furthermore investigated by 27Al solid-state magic-angle spinning (MAS) NMR. HfAl2 exhibits two Al resonances, one rather sharp and one significantly broadened signal, in line with the crystal structure and respective coordination environments. The members of the solid solution exhibit extremely broadened resonances due to the mixing of V and Al on the same crystallographic sites. For nominal Hf(V0.125Al0.875)2, however, two distinct sharp NMR signals were observed. This contrasts with the description of a solid solution. Therefore, single-crystal X-ray studies were conducted, showing that Hf(V0.125Al0.875)2 really is an ordered compound with the sum formula Hf4VAl7 (P3̅m1), which exhibits an, thus far, unknown superstructure of MgZn2.

Black Titania and Niobia within Ten Minutes - Mechanochemical Reduction of Metal Oxides with Alkali Metal Hydrides.

Partially or fully reduced transition metal oxides show extraordinary electronic and catalytic properties but are usually prepared by high temperature reduction reactions. This study reports the systematic investigation of the fast mechanochemical reduction of rutile-type TiO2 and H-Nb2 O5 to their partially reduced black counterparts applying NaH and LiH as reducing agents. Milling time and oxide to reducing agent ratio show a large influence on the final amount of reduced metal ions in the materials. For both oxides LiH shows a higher reducing potential than NaH. An intercalation of Li+ into the structure of the oxides was proven by PXRD and subsequent Rietveld refinements as well as 6 Li solid-state NMR spectroscopy. The products showed a decreased band gap and the presence of unpaired electrons as observed by EPR spectroscopy, proving the successful reduction of Ti4+ and Nb5+ . Furthermore, the developed material exhibits a significantly enhanced photocatalytic performance towards the degradation of methylene blue compared to the pristine oxides. The presented method is a general, time efficient and simple method to obtain reduced transition metal oxides.

Formation of the Sub-oxide Sc4Au2O1-x and the Drastically Negative 27Al NMR Shift in Sc2Al.

During attempts to synthesize Sc4AuAl in the cubic Gd4RhIn-type structure, the solid solution Sc2Au0.5Al0.5 in the PbCl2-type structure formed instead. Subsequently, the solid solution Sc2Au1-xAlx was investigated with respect to its existence range along with the structure types formed for different compositions with x = 0, 0.25, 0.5, 0.75, and 1. According to X-ray powder diffraction studies, Sc2Al and nominal Sc2Au0.25Al0.75 crystallized in the hexagonal Ni2In-type structure (P63/mmc), while Sc2Au0.5Al0.5, Sc2Au0.75Al0.25, and Sc2Au were found to crystallize in the orthorhombic PbCl2-type structure (Pnma). The crystal structures of Sc2Au and Sc2Au0.59(1)Al0.41(1) were refined from single-crystal data (Sc2Au: a = 648.0(1), b = 467.2(1), c = 835.2(2) pm, wR2 = 0.0382, 535 F2 values, 25 variables; Sc2Au0.59(1)Al0.41(1): a = 632.48(5), b = 472.16(3), c = 848.67(6) pm, wR2 = 0.0484, 540 F2 values, 21 variables). Contamination with air during the synthesis of Sc2Au led to the discovery of a compound adopting the cubic W4Co2C-type structure (stuffed cubic Ti2Ni type). Using Sc2O3 as a defined oxygen source led to samples with high amounts of Sc4Au2O1-x. All intermetallic compounds exhibited Pauli paramagnetic behavior in the investigated temperature range of 2.1 to 300 K, and no superconductivity was observed at low temperatures and low fields. Sc2Au and Sc2Al were investigated by 27Al and 45Sc solid-state NMR investigations. For Sc2Al, one signal was found in the 27Al NMR spectra in line with the crystal structure; however, an extremely negative resonance shift of δ = -673 ppm was observed. In both compounds, two Sc resonances were observed, in line with the proposed crystal structure. Finally, it was observed that the stability of Sc2Au in air is limited. This was investigated via thermal analysis and (temperature-dependent) powder X-ray diffraction. DFT calculations helped in assessing charge analysis, electronic properties, and chemical bonding.

Theoretical and 27Al NMR Spectroscopic Investigations of Binary Intermetallic Alkaline-Earth Aluminides.

The binary alkaline-earth aluminides AEAl2 (AE = Ca and Sr) and AEAl4 (AE = Ca-Ba) have been synthesized from the elements and investigated via powder X-ray diffraction experiments. CaAl2 adopts the cubic MgCu2-type structure (Fd3̅m), while SrAl2 crystallizes in the orthorhombic KHg2-type (Imma). LT-CaAl4 crystallizes with the monoclinic CaGa4-type (C2/m), while HT-CaAl4, SrAl4, and BaAl4 adopt the tetragonal BaAl4-type structure (I4/mmm). The close structural relation of the two CaAl4 polymorphs was established using a group-subgroup relation in the Bärnighausen formalism. In addition to the room-temperature and normal pressure phase of SrAl2, a high-pressure/high-temperature phase has been prepared using multianvil techniques, and its structural and spectroscopic parameters were determined. Elemental analysis by inductively coupled plasma mass spectrometry showed that no significant impurities with other elements besides the weighed ones are present and the chemical compositions match the synthesized ones. The title compounds have been furthermore investigated by 27Al solid-state magic angle spinning NMR experiments to validate the crystal structure and to gain information about the influence of the composition on the electron transfer and the NMR characteristics. This has also been investigated from a quantum chemical point of view using Bader charges, while the stabilities of the binary compounds in the three phase diagrams (Ca-Al, Sr-Al and Ba-Al) have been studied by calculations of formation energies per atom.

An Anionic Amido-Substituted Seven-Vertex Siliconoid Cluster.

The silanide [Si4 {N(SiMe3 )Dipp}3 ]- (1) transforms into the anionic siliconoid cluster [Si7 {N(SiMe3 )Dipp}3 ]- (2) with four unsubstituted silicon atoms as a contact ion pair with [K([18]crown-6)] in C6 D6 at room temperature within five weeks. Anion 2 was investigated by natural population analysis and visualization of intrinsic atomic orbitals. Magnetically induced current-density calculations of 2 revealed two distinct strong diatropic vortices that sum up in one direction and create a strongly shielded apical silicon atom in 2.

Triangular Arrangement of Ferromagnetic Iron Chains in the High-TC Ferromagnet TiFe1-x Os2+x B2.

Transition-metal borides (TMBs) containing Bn -fragment (n>3) have recently gained interest for their ability to enable exciting magnetic materials. Herein, we show that the B4 -containing TiFe0.64(1) Os2.36(1) B2 is a new ferromagnetic TMB with a Curie temperature of 523(2) K and a Weiss constant of 554(3) K, originating from the chain of M3 -triangles (M=64 %Fe+36 %Os). The new phase was synthesized from the elements by arc-melting, and its structure was elucidated by single-crystal X-ray diffraction. It belongs to the Ti1+x Os2-x RuB2 -type structure (space group P 6 ‾ 2 m, no. 189) and contains trigonal-planar B4 boron fragments [B-B distance of 1.87(4) Å] interacting with M3 -triangles [M-M distances of 2.637(8) Šand 3.0199(2) Å]. The experimental results were supported by computational calculations based on the ideal TiFeOs2 B2 composition, which revealed strong ferromagnetic interactions within and between the Fe3 -triangles. This discovery represents the first magnetically ordered Os-rich TMB, thus it will help expand our knowledge of the role of Os in low-dimensional magnetism of intermetallics and enable the design of such materials in the future.

Rare-Earth-Free Magnets: Enhancing Magnetic Anisotropy and Spin Exchange Toward High-TC Hf2MIr5B2 (M = Mn, Fe).

Designing new rare-earth-free (REF) permanent magnetic materials (PMM) to replace the high performing but critically restrained rare-earth-based PMM remains a great challenge to the scientific community. Here, we report on the rational design of new REF PMM, Hf2MIr5B2 (M = Fe, Mn) via a theory-experiment combined approach. Density functional theory (DFT) predicted strong interchain M-M spin-exchange coupling and large magnetocrystalline anisotropy energies (EMAE) for the new compounds, suggesting potential intrinsic PMM properties. Subsequent experimental bulk syntheses and magnetic characterizations established the highest ordering temperature (TC ∼ 900 K) for Hf2FeIr5B2 and the highest intrinsic coercivity (HC) value for Hf2MnIr5B2 (HC = 62.1 kA/m) reported to date for Ti3Co5B2-type compounds. Importantly, at room temperature both phases show significant coercivities due to intrinsic factors only, hinting at their huge potential to create REF PMM by improving extrinsic factors such as controlling the microstructure and the domain orientation.

Cu2ZnSbS4: A Thioantimonate(V) with Remarkably Strong Covalent Sb-S Bonding.

A new member to the A2IBIICIVX4 compound family, Cu2ZnSbS4, was synthesized successfully using ball milling and postannealing in H2S-atmosphere. For comparative purposes, Cu3SbS4 was additionally prepared using the same synthetic approach. As is common for A2IBIICIVX4 compounds, Cu2ZnSbS4 crystallizes isostructural to Cu3SbS4 in the stannite-type structure in space group I42m. Both antimony sulfides contain monovalent diamagnetic copper and are characterized by substantial covalent bonding. This is consistent with the 121Sb isomer shifts occurring for the Mössbauer spectra of Cu2ZnSbS4 (-7.71 mm s-1) and Cu3SbS4 (-7.68 mm s-1) which fall in the region of covalently bonded Sb(V) compounds. These spectroscopic results are supported by electronic structure calculations.

Ni[B2 (SO4 )4 ] and Co[B2 (SO4 )4 ]: Unveiling Systematic Trends in Phyllosilicate Analogue Borosulfates.

Borosulfates are compounds analogous to silicates, with heteropolyanionic subunits of vertex-linked (SO4 )- and (BO4 )-tetrahedra. In contrast to the immense structural diversity of silicates, the number of borosulfates is yet very limited and the extent of their properties is still unknown. This is particularly true for representatives with phyllosilicate and tectosilicate analogue anionic substructures. Herein, we present Ni[B2 (SO4 )4 ] and Co[B2 (SO4 )4 ], two new borosulfates with phyllosilicate analogue topology. While the anionic subunits of both structures are homeotypic, the positions of the charge compensating cations differ significantly: NiII is located between the borosulfate layers, while CoII -in contrast-is embedded within the layer. Detailed analysis of these two structures based on single-crystal X-ray diffraction, magnetochemical investigations, X-ray photoelectron spectroscopy, and quantum chemical calculations, unveiled the reasons for this finding. By in silico comparison with other divalent borosulfates, we uncovered systematic trends for phyllosilicate analogues leading to the prediction of new species.

Physical and Magnetocaloric Properties of TbPdAl2 and the Ferromagnetic Solid Solution Tb1-xLuxPdAl2 (x = 0.1-0.9).

TbPdAl2 and the solid solution Tb1-xLuxPdAl2 (x = 0.1-1) have been synthesized via arc-melting techniques using the elements as starting materials and crystallize in the orthorhombic MgCuAl2-type structure (Cmcm). As expected, the unit cell volumes decrease due to the lanthanide contraction from the Tb to Lu compounds, thus showing Vegard behavior because of the differences of the ionic radii of the trivalent rare-earth cations. TbPdAl2 orders ferromagnetically below TC = 85.5(5) K and shows partial magnetic saturation already at low fields. The magnetic phase transition has been additionally investigated by heat capacity measurements, showing a broadened λ anomaly at THC = 83.2(1) K. The electrical resistivity is almost linear above TC, indicating dominant electron-phonon interactions. Below the ordering temperature, electron-spin wave scattering with a ρ ∼ T2 behavior is evident. In the solid solution Tb1-xLuxPdAl2 (x = 0-1), the ferromagnetic Curie temperatures decrease in a linear fashion with increasing Lu content. Investigations of the magnetocaloric properties of TbPdAl2 obtained a maximum magnetic entropy change of -ΔSMmax = 1.2, 2.2, 3.1, and 3.6 J kg-1 K-1 for the field changes of ΔH = 10, 20, 50, and 70 kOe, respectively. The rather low values are caused by entropy losses due to hysteresis behavior. The relative cooling power for TbPdAl2, therefore, also exhibits comparably low values of 32, 81, 142, and 178 J kg-1.

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.

Intermetallic RE6T5Al7 Phases (RE = Sc, Y, Ce-Nd, Sm, Gd-Lu; T = Ru, Ir): Diversity in their Magnetic, Magnetocaloric, and Critical Properties.

Over 20 new compounds of the RE6T5Al7 series (RE = Sc, Y, Ce-Nd, Sm, Gd-Lu; T = Ru, Ir; Yb6Ir5Ga7 type structure; superstructure of MgZn2; fully ordered Nb6.4Ir4Al7.6 type) have been synthesized. They crystallize in the hexagonal crystal system with space group P63/mcm. Their lattice parameters are in the ranges of a = 935-963 and c = 851-874 pm for the RE6Ru5Al7 and a = 913-966 and c = 825-865 pm for the RE6Ir5Al7 series. Four structures (Ho6Ru5Al7, Yb6Ru4.68(1)Al7.32(1), Sc6Ir5Al7, and Ho6Ir4.53(1)Al7.47(1)) have been refined from single-crystal data, indicating fully ordered structures for Ho6Ru5Al7 and Sc6Ir5Al7; however, T/Al mixing was observed on one crystallographic site for Ho6Ir4.53(1)Al7.47(1) and on two sites for Yb6Ru4.68(1)Al7.32(1). The Sc-, Y-, and Lu-containing compounds exhibit Pauli paramagnetism in line with a filled d band for Ru and Ir. Ce6Ru5Al7 exhibits mixed-valent behavior, while Yb6Ru5Al7 is solely trivalent. The other compounds exhibit paramagnetism and ferromagnetic phase transitions up to temperatures of TC = 83.4(1) K for Gd6Ru5Al7. In addition to the basic magnetic characterizations and studies of the electrical resistivity and heat capacity, the magnetocaloric properties of Gd6Ru5Al7, Tb6Ru5Al7, and Dy6Ru5Al7 have been investigated, revealing magnetic entropy changes of -ΔSMmax = 6.2(1), 7.7(1), and 5.4(1) J kg-1 K-1 (0 → 5 T) and relative cooling powers RCP = 242, 207, and 135 J kg-1, respectively. For a deeper insight into the second-order magnetic phase transitions, the critical behavior was investigated according to the scaling hypothesis. The critical behavior of Gd6Ru5Al7 is in accordance with the mean-field theory; the critical exponents of Tb6Ru5Al7 and Dy6Ru5Al7, however, deviate strongly from this universality class. For comparison of the structural and magnetic properties, the thus far unstudied members of the RERuAl series (RE = Sc, Y, Sm, Gd-Lu; MgZn2 type) have additionally been prepared and characterized.

Correlations of Crystal and Electronic Structure via NMR and X-ray Photoelectron Spectroscopies in the RETMAl2 (RE = Sc, Y, La-Nd, Sm, Gd-Tm, Lu; TM = Ni, Pd, Pt) Series.

A total of 35 intermetallic aluminum compounds have been synthesized from the elements via arc melting and characterized by powder X-ray diffraction. A total of 15 of them have been previously reported; however, detailed property investigations were missing. Compounds of the RETMAl2 (rare earth metal RE = Sc, Y, La-Nd, Sm, Gd-Tm, Lu) series with transition metal TM = Ni, Pd, and Pt crystallize isostructurally in the orthorhombic MgCuAl2 type structure ( Cmcm, oC16, fc2). Single-crystal X-ray diffraction investigations were conducted on YNiAl2, LaNiAl2, YPdAl2, ScPtAl2, and YPtAl2. The TM and Al atoms form a [TMAl2]δ- polyanion, the RE atoms reside in cavities within the framework. While the Sc, Y, La, and Lu compounds exhibit Pauli-paramagnetic behavior, consistent with all atoms being closed shell, the other RETMAl2 compounds show paramagnetism along with magnetic ordering at low temperatures, in line with an open-shell trivalent oxidation state for the RE atoms. Solid-state 27Al NMR investigations were carried out on the Pauli-paramagnetic samples, all showing only a single central transition, in line with one crystallographic site for the respective atoms. The observed quadrupolar coupling constants and electric-field-gradient asymmetry parameters were found to be in good agreement with the density-functional-theory-calculated values. Isotropic resonance shifts are dominated by the Fermi-contact interactions with s-conduction electron densities at the Fermi edge (Knight shifts). The bonding characteristics mirror the electronic density of states and crystal chemistry of the family of intermetallic compounds under consideration. Both the Knight shifts and quadrupolar coupling constants can be predicted based on element-specific increments.

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.

Structural Characterization of Intermetallic Compounds by 27Al Solid State NMR Spectroscopy.

Intermetallic compounds are of broad interest for solid state chemists, condensed matter physicists, and material scientists due to their intriguing crystal chemistry, their physical properties, and their potential applications, ranging from lab curiosities to everyday objects. To characterize and understand the properties of new compounds and novel materials, the availability of structural information, particularly single-crystal X-ray diffraction data, is a mandatory prerequisite. Especially when it comes to the formation of compounds with deficient or mixed site occupancies, superstructures, or representatives crystallizing in other, thus far unknown structure types, a complementary method for structural analysis is of great value. Solid state nuclear magnetic resonance spectroscopy has been a valuable tool in many areas of chemistry, being an element-selective, site-specific, and inherently quantitative tool for detailed structural characterization. Magic-angle spinning conditions eliminate or reduce the effect of anisotropic interactions in the solid state, producing high-resolution spectra. Until recently, 27Al NMR studies of intermetallic aluminum compounds have been relatively sparse and mostly limited to binary systems. In this Account, we will summarize the current state of the art of high-resolution 27Al NMR in intermetallic compounds focusing on recent research efforts in our laboratories and the interpretation of NMR parameters in terms of the structural details of the compounds investigated. Besides theoretical aspects of 27Al NMR spectroscopy, short paragraphs on experimental details and the crystal chemistry of the discussed compounds are given. In the main part of this Account, we focus on three key aspects: (i) crystal structure validation, (ii) structural disorder and mixed site occupancies, and (iii) the electronic structure, all of which can be investigated by spectroscopic means. For the first part, we have chosen the ternary equiatomic compounds CaAuAl (TiNiSi type), BaAuAl (LaIrSi type), and Ba3Pt4Al4 (own type). Structural disorder and mixed site occupancies have been probed in the ScTAl series (T = Cr, Ru, Ag, Re) crystallizing in the TiNiSi, HfRhSn, and MgZn2-type structures. Also Na2Au3Al and the Heusler compounds, Sc(T0.5T'0.5)2Al (T = T' = Ni, Pd, Pt, Cu, Ag, Au), have been used for structure validation purposes, based on the number and signal area ratios of the resonances observed and on the comparison between experimental and theoretically calculated nuclear electric quadrupolar interaction parameters. Electronic structure information available from 27Al magnetic shielding will be discussed based on experimental data obtained for the RET5Al2 series (RE = Y, Lu; T = Pd, Pt), the extended RE10TAl3 series (RE = Y, Lu; T = Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), and the ordered Heusler compounds ScT2Al (T = Ni, Pd, Pt, Cu, Ag, Au).

The High-Pressure Oxide Tb3 O5 and its Non-Centrosymmetric Low-Temperature Polymorph-A Comprehensive Study.

In this article, the first thoroughly characterized mixed-valent binary rare earth oxide synthesized under high-pressure/high-temperature conditions, and its low-temperature polymorph are reported. Crystalline HT-HP-Tb3 O5 has been prepared from an equimolar mixture of Tb4 O7 and Tb2 O3 under reaction conditions of 8 GPa and 1323 K. Single-crystal X-ray structure determination showed that HT-HP-Tb3 O5 crystallizes in the orthorhombic space group Pnma, isopointal to the ß-Yb5 Sb3 -type structure. Temperature-dependent measurements of the magnetic susceptibility showed that HT-HP-Tb3 O5 is a Curie-Weiss paramagnet. The observed effective magnetic moment of µeff =9.21(2) µB per formula unit fits well to the calculated moment of µcalc =9.17 µB . Low-field measurements revealed antiferromagnetic ordering at TN =3.6(1) K. Heat capacity measurements indicated an intrinsic structural phase transition of HT-HP-Tb3 O5 at low temperature, which was confirmed by synchrotron X-ray powder diffraction data recorded at 2 K. The metastable high-pressure modification HT-HP-Tb3 O5 undergoes a translationengleiche transition from space group Pnma to Pn21 a (non-standard setting of Pna21 ), leading to the low-temperature polymorph LT-HP-Tb3 O5 by loss of a mirror plane (displacive phase transition).