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Kagome compounds have garnered attention in the past few years for their intriguing magnetic properties arising from spin frustration dictated by the geometry of the Kagome sublattice. In this paper, we highlight the success of the unconventional hydride route for the fast and easy synthesis of the Kagome compound KV6Sb6. High-temperature in situ powder x-ray diffraction (PXRD) studies proved to be useful in hinting at the existence of KV6Sb6, identifying its synthesis conditions, and understanding the reaction mechanism. The crystal structure for KV6Sb6 was determined from high-resolution PXRD data. The compound has a layered structure [R¯3m,a=5.5318(9)Å, c=34.23(3)Å, V=907.0(8)Å3, Z=3 at room temperature] and features a Kagome bilayer of V atoms. KV6Sb6 is isostructural to the previously reported RbV6Sb6 and CsV6Sb6 compounds. KV6Sb6 is thermally stable in vacuum up to 1173 K, as evident from the high-temperature in situ PXRD and differential scanning calorimetric analysis. Investigation of magnetic properties for KV6Sb6 between 2 and 300 K reveals temperature-independent paramagnetism and an absence of superconductivity, like the Rb and Cs analogs. Furthermore, we compare the magnetic properties of KV3Sb5, another ternary Kagome compound, synthesized via two different methods: the hydride route and the traditional route from elements. Low-temperature transport property measurements of KV6Sb6 indicate metallic behavior and an intrinsically low thermal conductivity of 1.0WK−1m−1 at 300 K. The layered structure of KV6Sb6 makes it an attractive candidate for deintercalation and doping studies to tune both magnetic and transport properties, laying a foundation for further studies.more » « less
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Combined experimental and density functional theory (DFT) study of Pr0.75Gd0.25ScGe and its hydride (Pr0.75Gd0.25ScGeH) reveals intricacies of composition-structure-property relationships in those distinctly layered compounds. Hydrogenation of the intermetallic parent, crystalizing in a tetragonal CeScSi-type structure, leads to an anisotropic volume expansion, that is, a(=b) lattice parameter decreases while the lattice expands along the c direction, yielding a net increase of cell volume. DFT calculations predict an antiparallel coupling of localized Gd and Pr magnetic moments in both materials at the ground state. While experiments corroborate this for the parent compound, there is no conclusive experimental proof for the hydride, where Pr moments do not order down to 3 K. DFT results also reveal that rare-earth – hydrogen interactions reduce spin-polarization of the Pr and Gd 5d and Sc 3d states at the Fermi energy, disrupt indirect exchange interactions mediated by conduction electrons, dramatically reduce the magnetic ordering temperature, and open a pseudo-gap in the majority-spin channel. Both experiments and theory show evidence of Kondo-like behavior in the hydride in the absence of an applied magnetic field, whereas increasing the field promotes magnetic ordering and suppresses Kondo-like behavior.more » « less
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Magnetic ionic liquids (MILs) are a subclass of ionic liquids that possess a paramagnetic metal within their chemical structure, making them susceptible to external magnetic fields. A total of twenty-four (24) MILs were prepared and characterized to investigate the effect of the ligand, cation and anion on the physiochemical properties of acetylacetonate-based MILs. It was found that thermal stabilities as high as 260 °C could be achieved by incorporating aromatic moieties in the anion structure. Additionally, the magnetic moment could be modulated by simply changing the transition metal in the anion. Magnetic moment values of 2.8 μ B , 4.5 μ B and 5.6 μ B were obtained by using Ni( ii ), Co( ii ), and Mn( ii ) as the metal centers, respectively. Furthermore, the viscosity of the MILs could be tailored from a few hundred centipoise to several thousand centipoise, increasing their potential applications in numerous interdisciplinary fields. Moreover, the MILs synthesized in this study were found to be insoluble in water at a MIL-to-solvent ratio of 0.01% (w/v), making them potentially useful in targeted separations, where very hydrophobic solvents are highly desired.more » « less