Fe- and B-Chains in the Ti5-xFe1-yOs6+x+yB6 Structure Type Derived from Chemical Twinning of the Nb1-xOs1+xB Type: Experimental and Computational Investigations.

The complex metal-rich boride Ti5-xFe1-yOs6+x+yB6 (0 < x,y < 1), crystallizing in a new structure type (space group Cmcm, no. 63), was prepared by arc-melting. The new structure contains both isolated boron atoms and zigzag boron chains (B-B distance of 1.74 Å), a rare combination among metal-rich borides. In addition, the structure also contains Fe-chains running parallel to the B-chains. Unlike in previously reported structures, these Fe-chains are offset from each other and arranged in a triangular manner with intrachain and interchain distances of 2.98 and 6.69 Å, respectively. Density functional theory (DFT) calculations predict preferred ferromagnetic interactions within each chain but only small energy differences for different magnetic interactions between them, suggesting a potentially weak long-range order. This new structure offers the opportunity to study new configurations and interactions of magnetic elements for the design of magnetic materials.

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.

It Runs in the BaAl4 Family: Relating the Structure and Properties of Middle Child Ln2Co3Ge5 (Ln = Pr, Nd, and Sm) to its Siblings LnCo2Ge2 and LnCoGe3.

The BaAl4 prototype structure and its derivatives have been identified to host several topological quantum materials and noncentrosymmetric superconductors. Single crystals up to ∼3 mm × 3 mm × 5 mm of Ln2Co3Ge5 (Ln = Pr, Nd, and Sm) are obtained via flux growth utilizing Sn as metallic flux. The crystal structure is isostructural to the Lu2Co3Si5 structure type in the crystallographic space group C2/c. The temperature-dependent magnetization indicates magnetic ordering at 30 K for all three compounds. Pr2Co3Ge5 and Nd2Co3Ge5 exhibit complex magnetic behavior with spin reorientations before ordering antiferromagnetically around 6 K, whereas Sm2Co3Ge5 shows a clear antiferromagnetic behavior at 26 K. The structures and properties of Ln2Co3Ge5 (Ln = Pr, Nd, and Sm) are compared to those of the ThCr2Si2 and BaNiSn3 structure types. Herein, we present the optimized crystal growth, structure, and physical properties of Ln2Co3Ge5 (Ln = Pr, Nd, and Sm).

Evidence of a coupled electron-phonon liquid in NbGe2.

Whereas electron-phonon scattering relaxes the electron's momentum in metals, a perpetual exchange of momentum between phonons and electrons may conserve total momentum and lead to a coupled electron-phonon liquid. Such a phase of matter could be a platform for observing electron hydrodynamics. Here we present evidence of an electron-phonon liquid in the transition metal ditetrelide, NbGe2, from three different experiments. First, quantum oscillations reveal an enhanced quasiparticle mass, which is unexpected in NbGe2 with weak electron-electron correlations, hence pointing at electron-phonon interactions. Second, resistivity measurements exhibit a discrepancy between the experimental data and standard Fermi liquid calculations. Third, Raman scattering shows anomalous temperature dependences of the phonon linewidths that fit an empirical model based on phonon-electron coupling. We discuss structural factors, such as chiral symmetry, short metallic bonds, and a low-symmetry coordination environment as potential design principles for materials with coupled electron-phonon liquid.

Antiferromagnetic Order and Spin-Canting Transition in the Corrugated Square Net Compound Cu3(TeO4)(SO4)·H2O.

Strongly correlated electrons in layered perovskite structures have been the birthplace of high-temperature superconductivity, spin liquids, and quantum criticality. Specifically, the cuprate materials with layered structures made of corner-sharing square-planar CuO4 units have been intensely studied due to their Mott insulating ground state, which leads to high-temperature superconductivity upon doping. Identifying new compounds with similar lattice and electronic structures has become a challenge in solid-state chemistry. Here, we report the hydrothermal crystal growth of a new copper tellurite sulfate, Cu3(TeO4)(SO4)·H2O, a promising alternative to layered perovskites. The orthorhombic phase (space group Pnma) is made of corrugated layers of corner-sharing CuO4 square-planar units that are edge-shared with TeO4 units. The layers are linked by slabs of corner-sharing CuO4 and SO4. Using both the bond valence sum analysis and magnetization data, we find purely Cu2+ ions within the layers but a mixed valence of Cu2+/Cu+ between the layers. Cu3(TeO4)(SO4)·H2O undergoes an antiferromagnetic transition at TN = 67 K marked by a peak in the magnetic susceptibility. Upon further cooling, a spin-canting transition occurs at T* = 12 K, evidenced by a kink in the heat capacity. The spin-canting transition is explained on the basis of a J1-J2 model of magnetic interactions, which is consistent with the slightly different in-plane superexchange paths. We present Cu3(TeO4)(SO4)·H2O as a promising platform for the future doping and strain experiments that could tune the Mott insulating ground state into superconducting or spin liquid states.

An Old Dog with New Tricks - Additions to the Cesium Lithium Chloride System: Cs3Li2Cl5 and the Hydrated Cs3LiCl4 · 4H2O.

The CsCl/LiCl system has been studied for over a century now. Numerous phases have been predicted - only three have hitherto been found. We present the synthesis and single-crystal structure of the cesium lithium pentachloride Cs3Li2Cl5, predicted earlier but with a different structure. The anhydrous new phase readily reacts to Cs3LiCl4 · 4H2O in air. The tetrahydrate can also be obtained through the simplest, most inexpensive and green synthesis possible: an immediate, room-temperature mechanosynthesis from only CsCl and LiCl (3 : 1) in air. Differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA), as well as in situ temperature-dependent powder X-ray diffraction studies on this second ever reported ternary alkali chloride hydrate allowed for a revision of the CsCl/LiCl phase diagram. Density of states and total energy calculations further elucidate the new alkali chlorides and update the relative stability of previous structure predictions.

Graphene- and Phosphorene-like Boron Layers with Contrasting Activities in Highly Active Mo2B4 for Hydrogen Evolution.

Two different boron layers, flat (graphene-like) and puckered (phosphorene-like), found in the crystal structure of Mo2B4 show drastically different activities for hydrogen evolution, according to Gibbs free energy calculations of H-adsorption on Mo2B4. The graphene-like B layer is highly active, whereas the phosphorene-like B layer performs very poorly for hydrogen evolution. A new Sn-flux synthesis permits the rapid single-phase synthesis of Mo2B4, and electrochemical analyses show that it is one of the best hydrogen evolution reaction active bulk materials with good long-term cycle stability under acidic conditions. Mo2B4 compensates its smaller density of active sites if compared with highly active bulk MoB2 (which contains only the more active graphene-like boron layers) by a 5-times increase of its surface area.

Boron: Enabling Exciting Metal-Rich Structures and Magnetic Properties.

Boron's unique chemical properties and its reactions with metals have yielded the large class of metal borides with compositions ranging from the most boron-rich YB66 (used as monochromator for synchrotron radiation) up to the most metal-rich Nd2Fe14B (the best permanent magnet to date). The excellent magnetic properties of the latter compound originate from its unique crystal structure to which the presence of boron is essential. In general, knowing the crystal structure of any given extended solid is the prerequisite to understanding its physical properties and eventually predicting new synthetic targets with desirable properties. The ability of boron to form strong chemical bonds with itself and with metallic elements has enabled us to construct new structures with exciting properties. In recent years, we have discovered new boride structures containing some unprecedented boron fragments (trigonal planar B4 units, planar B6 rings) and low-dimensional substructures of magnetically active elements (ladders, scaffolds, chains of triangles). The new boride structures have led to new superconducting materials (e.g., NbRuB) and to new itinerant magnetic materials (e.g., Nb6Fe1-xIr6+xB8). The study of boride compounds containing chains (Fe-chains in antiferromagnetic Sc2FeRu5B2), ladders (Fe-ladders in ferromagnetic Ti9Fe2Rh18B8), and chains of triangles (Cr3 chains in ferrimagnetic and frustrated TiCrIr2B2) of magnetically active elements allowed us to gain a deep understanding of the factors (using density functional theory calculations) that can affect magnetic ordering of such low-dimensional magnetic units. We discovered that the magnetic properties of phases containing these magnetic subunits can be drastically tuned by chemical substitution within the metallic nonmagnetic network. For example, the small hysteresis (measure of magnetic energy storage) of Ti2FeRh5B2 can be successively increased up to 24-times by gradually substituting Ru for Rh, a result that was even surpassed (up to 54-times the initial value) for Ru/Ir substitutions. Also, the type of long-range magnetic interactions could be drastically tuned by appropriate substitutions in the metallic nonmagnetic network as demonstrated using both experimental and theoretical methods. It turned out that Ru-rich and valence electron poor metal borides adopting the Ti3Co5B2 or the Th7Fe3 structure types have dominating antiferromagnetic interactions, while in Rh-rich (or Ir-rich) and valence electron rich phases ferromagnetic interactions prevail, as found, for example, in the Sc2FeRu5-xRhxB2 and FeRh6-xRuxB3 series. Fascinatingly, boron clusters (e.g., B6 rings) even directly interact in some cases with the magnetic subunits, an interaction which was found to favor the Fe-Fe magnetic exchange interactions in the ferromagnetic Nb6Fe1-xIr6+xB8. Using less expensive transition metals, we have recently predicted new itinerant magnets, the experimental proof of which is still pending. Furthermore, new structures have been discovered, all of which are being studied experimentally and computationally with the aim of finding new superconductors, magnets, and mechanically hard materials. A new direction is being pursued in our group, as binary and ternary transition metal borides show great promise as efficient water splitting electrocatalysts at the micro- and nanoscale.

Titanium Sulfides as Intercalation-Type Cathode Materials for Rechargeable Aluminum Batteries.

We report the electrochemical intercalation-extraction of aluminum (Al) in the layered TiS2 and spinel-based cubic Cu0.31Ti2S4 as the potential cathode materials for rechargeable Al-ion batteries. The electrochemical characterizations demonstrate the feasibility of reversible Al intercalation in both titanium sulfides with layered TiS2 showing better properties. The crystallographic study sheds light on the possible Al intercalation sites in the titanium sulfides, while the results from galvanostatic intermittent titration indicate that the low Al3+ diffusion coefficients in the sulfide crystal structures are the primary obstacle to facile Al intercalation-extraction.

Boron-Dependency of Molybdenum Boride Electrocatalysts for the Hydrogen Evolution Reaction.

Molybdenum-based materials have been considered as alternative catalysts to noble metals, such as platinum, for the hydrogen evolution reaction (HER). We have synthesized four binary bulk molybdenum borides Mo2 B, α-MoB, ß-MoB, and MoB2 by arc-melting. All four phases were tested for their electrocatalytic activity (linear sweep voltammetry) and stability (cyclic voltammetry) with respect to the HER in acidic conditions. Three of these phases were studied for their HER activity and by X-ray photoelectron spectroscopy (XPS) for the first time; MoB2 and ß-MoB show excellent activity in the same range as the recently reported α-MoB and ß-Mo2 C phases, while the molybdenum richest phase Mo2 B show significantly lower HER activity, indicating a strong boron-dependency of these borides for the HER. In addition, MoB2 and ß-MoB show long-term cycle stability in acidic solution.

Direct Chemical Fine-Tuning of Electronic Properties in Sc2 Ir6-x Pdx B.

Crystal orbital Hamilton population (COHP) bonding analysis has predicted that ScPd3 B0.5 is the least stable compound of the entire series Sc2 Ir6-x Pdx B. Here, we report a systematic study of Sc2 Ir6-x Pdx B (x=3, 5 and 6) by means of 11 B nuclear magnetic resonance (NMR), Knight shift (K) and nuclear spin-lattice relaxation rate (1/T1 ). NMR results combined with theoretical band structure calculations provide a measure of s- and non-s-character Fermi-level density of states. We present direct evidence that the enhanced s-state character of the Fermi level density of states (DOS) in ScPd3 B0.5 reduces the strength of the B 2p and Pd 4d hybridized states across the entire Sc2 Ir6-x Pdx B series. This hybridization strength relates to the opening of a deep pseudogap in the density of states of Sc2 IrPd5 B and the chemical bonding instability of ScPd3 B0.5 . This study is an experimental realization of a chemical fine-tuning of the electronic properties in intermetallic perovskites.

Electronic pseudogap-driven formation of new double-perovskite-like borides within the Sc2Ir6-xTxB (T = Pd, Ni; x = 0-6) series.

Analysis of the electronic density of states of the hypothetical ternary double-perovskite-like phases "Sc2T6B (T = Ir, Pd, Ni)" reveals the presence of deep and large pseudogaps between 61 and 68 valence electrons (VE) as well as a strong peak at 69 VEs. Subsequently, crystal orbital Hamilton population (COHP) bonding analysis shows that the heteroatomic T-B and Sc-T interactions are optimized in Sc2Ir6B (63 VE) but not in "Sc2Pd6B (69 VE)" and "Sc2Ni6B (69 VE)", thus indicating less stability for these VE-richer phases. These findings point out the possibility of discovering new double-perovskite-like borides through chemical substitution and lead to the study of the Sc2Ir6-xPdxB and Sc2Ir6-xNixB (x = 0-6; VE = 63-69) series, for which powder samples and single crystals were synthesized by arc melting the elements. Superstructure reflections were observed in the powder diffractograms of Sc2Ir6-xPdxB and Sc2Ir6-xNixB for x = 0-5 and VE = 63-68, thereby showing that these phases crystallize in the double-perovskite-like Ti2Rh6B-type structure (space group Fm3̅m, Z = 4). Single-crystal and Rietveld refinement results confirm and extend these findings because Pd (or Ni) is found to mix exclusively with Ir in all quaternary compositions. For x = 6, no superstructure reflections were observed, in accordance with the theoretical expectation for the 69 VE phases.