Synthesis of Zintl Phase Metal Silicide Thermoelectric Materials in Magnesium/Zinc Flux.

Zintl phases have potential applications as thermoelectric materials for power generation and cooling owing to their complex crystal structures and unique electronic properties. We carried out reactions of silicon with barium and strontium in excess Mg/Zn flux to synthesize (Ba/Sr)5+xMg19-xSi12 Zintl phases, investigating the effect of varying Ba/Sr ratio on site mixing and thermoelectric properties. (Ba/Sr)5+xMg19-xSi12 compounds with 0 < x < 3 are charge-balanced Zintl phases which adopt the hexagonal Ho5Ni19P12 structure type (space group P6̅2m). Density of states calculations indicate that these materials are semimetals. Single-crystal X-ray diffraction data and elemental analysis for Ba5Mg19Si12, Ba4.86Sr2.94Mg16.20Si12, Ba3.63Sr4.20Mg16.17Si12, Ba1.93Sr5.99Mg16.08Si12, and Sr7.82Mg16.18Si12 show occupation of barium and strontium cations in Ho sites, while strontium mixes with magnesium on a specific Ni site. Powder XRD data of products show that they are single phase throughout the sample. Thermoelectric measurements indicate that increasing strontium content and mixing on three cation sites decreases thermal conductivity; it is hypothesized that improved overall thermoelectric behavior is likely due to the rattling of the Sr cations in their positions.

Isoelectronic perturbations to f-d-electron hybridization and the enhancement of hidden order in URu2Si2.

Electrical resistivity measurements were performed on single crystals of URu2-x Os x Si2 up to x = 0.28 under hydrostatic pressure up to P = 2 GPa. As the Os concentration, x, is increased, 1) the lattice expands, creating an effective negative chemical pressure Pch(x); 2) the hidden-order (HO) phase is enhanced and the system is driven toward a large-moment antiferromagnetic (LMAFM) phase; and 3) less external pressure Pc is required to induce the HO→LMAFM phase transition. We compare the behavior of the T(x, P) phase boundary reported here for the URu2-x Os x Si2 system with previous reports of enhanced HO in URu2Si2 upon tuning with P or similarly in URu2-x Fe x Si2 upon tuning with positive Pch(x). It is noteworthy that pressure, Fe substitution, and Os substitution are the only known perturbations that enhance the HO phase and induce the first-order transition to the LMAFM phase in URu2Si2 We present a scenario in which the application of pressure or the isoelectronic substitution of Fe and Os ions for Ru results in an increase in the hybridization of the U-5f-electron and transition metal d-electron states which leads to electronic instability in the paramagnetic phase and the concurrent formation of HO (and LMAFM) in URu2Si2 Calculations in the tight-binding approximation are included to determine the strength of hybridization between the U-5f-electron states and the d-electron states of Ru and its isoelectronic Fe and Os substituents in URu2Si2.

Widely Varying Kondo and Magnetic Interactions in Molecule Gold Nanostructured Materials by Changing the Gold Nanoarchitecture.

Delocalized-localized electron interactions are central to strongly correlated electron phenomena. Here, we study the Kondo effect, a prototypical strongly correlated phenomena, in a tunable fashion using gold nanostructures (nanoparticle, NP, and nanoshell, NS) + molecule cross-linkers (butanedithiol, BDT). NP films exhibit hallmark signatures of the Kondo effect, including (1) a log temperature resistance upturn as temperature decreases in a metallic regime, and (2) zero-bias conductance peaks (ZBCPs) that are well fit by a Frota function near a percolation insulator transition, previously used to model Kondo peaks observed using tunnel junctions. Remarkably, NP + NS films exhibit ZBCPs that persist to >220 K, i.e., >10-fold higher than that in NP films. Magnetic measurements reveal that moments in NP powders align, and in NS powders, they antialign at low temperatures. Based on these observations, we propose a mechanism in which varying such material nanobuilding blocks can modify electron-electron interactions to such a large degree.

Ground-State Spin Dynamics in d1 Kagome-Lattice Titanium Fluorides.

Many quantum magnetic materials suffer from structural imperfections. The effects of structural disorder on bulk properties are difficult to assess systematically from a chemical perspective due to the complexities of chemical synthesis. The recently reported S = 1/2 kagome lattice antiferromagnet, (CH3NH3)2NaTi3F12, 1-Ti, with highly symmetric kagome layers and disordered interlayer methylammonium cations, shows no magnetic ordering down to 0.1 K. To study the impact of structural disorder in the titanium fluoride kagome compounds, (CH3NH3)2KTi3F12, 2-Ti, was prepared. It presents no detectable structural disorder and only a small degree of distortion of the kagome lattice. The methylammonium disorder model of 1-Ti and order in 2-Ti were confirmed by atomic-resolution transmission electron microscopy. The antiferromagnetic interactions and band structures of both compounds were calculated based on spin-polarized density functional theory and support the magnetic structure analysis. Three spin-glass-like (SGL) transitions were observed in 2-Ti at 0.5, 1.4, and 2.3 K, while a single SGL transition can be observed in 1-Ti at 0.8 K. The absolute values of the Curie-Weiss temperatures of both 1-Ti (-139.5(7) K) and 2-Ti (-83.5(7) K) are larger than the SGL transition temperatures, which is indicative of geometrically frustrated spin glass (GFSG) states. All the SGL transitions are quenched with an applied field >0.1 T, which indicates novel magnetic phases emerge under small applied magnetic fields. The well-defined structure and the lack of structural disorder in 2-Ti suggest that 2-Ti is an ideal model compound for studying GFSG states and the potential transitions between spin liquid and GFSG states.

Crystal Growth and Physical Properties of Hybrid CoSn-YCo6Ge6 Structure Type LnxCo3(Ge1-ySny)3 (Ln = Y, Gd).

There is an ongoing interest in kagome materials because they offer tunable platforms at the intersection of magnetism and electron correlation. Herein, we examine single crystals of new kagome materials, LnxCo3(Ge1-ySny)3 (Ln = Y, Gd; y = 0.11, 0.133), which were produced using the Sn flux-growth method. Unlike many of the related chemical analogues with the LnM6X6 formula (M = transition metal and X = Ge, Sn), the Y and Gd analogues crystallize in a hybrid YCo6Ge6/CoSn structure, with Sn substitution. While the Y analogue displays temperature-independent paramagnetism, magnetic measurements of the Gd analogue reveal a magnetic moment of 8.48 µB, indicating a contribution from both Gd and Co. Through anisotropic magnetic measurements, the direction of Co-magnetism can be inferred to be in plane with the kagome net, as the Co contribution is only along H//a. Crystal growth and structure determination of YxCo3(Ge,Sn)3 and GdxCo3(Ge,Sn)3, two new hybrid kagome materials of the CoSn and YCo6Ge6 structure types. Magnetic properties, heat capacity, and resistivity on single crystals are reported.

Structures and Magnetic Properties of K2Pd4U6S17, K2Pt4U6S17, Rb2Pt4U6S17, and Cs2Pt4U6S17 Synthesized Using the Boron-Chalcogen Mixture Method.

A series of A2M4U6S17 (A = alkali metal; M = Pd, Pt) compounds, specifically K2Pd4U6S17, K2Pt4U6S17, Rb2Pt4U6S17, and Cs2Pt4U6S17, were synthesized using the combined boron-chalcogen mixture and molten flux crystal growth methods. The formation of rubidium- and cesium-containing analogues resulted from a in situ alkali polysulfide flux formed from alkali carbonates. The successful synthesis of single crystals of the title compounds allowed for their structural characterization by single-crystal X-ray diffraction. The structure determination revealed disorder of the alkali cations in Rb2Pt4U6S17 and Cs2Pt4U6S17, while the potassium cations in K2Pd4U6S17 and K2Pt4U6S17 were fully ordered. Magnetic measurements were performed on samples of K2Pt4U6S17, Rb2Pt4U6S17, and Cs2Pt4U6S17 that contained small amounts of paramagnetic ß-US2 and diamagnetic PtS. Antiferromagnetic order was observed at TN = 9.1 K for K2Pt4U6S17. No long-range magnetic order was observed for Rb2Pt4U6S17 and Cs2Pt4U6S17. Uranium moments of 2.5, 2.6, and 2.6 µB were measured for K2Pt4U6S17, Rb2Pt4U6S17, and Cs2Pt4U6S17, respectively.

Flux Growth of Cerium Nickel Gallides Studied by In Situ Neutron Diffraction.

Reactions of cerium and nickel in excess molten gallium were monitored by neutron diffraction during heating and cooling. The formation of binary intermediates CeGa2 and Ni2Ga3 was observed during heating. During cooling of the molten mixture from 900 °C, precipitation of BaAl4-type CeNi0.74Ga3.26 occurred at 850 °C. Upon cooling to 650 °C, this compound reacted in the flux to form Ce2NiGa10 and then Ce2NiGa12, the latter of which persisted to room temperature. Making use of this information, subsequent reactions were quenched at 750 °C to isolate crystals of CeNi0.74Ga3.26 for further study. Similar reactions replacing Ce with La and quenching above 750 °C yielded LaNi0.35Ga3.65 crystals. Magnetic susceptibility studies on CeNi0.74Ga3.26 indicate that the cerium is trivalent; the Ce3+ moments undergo a strongly anisotropic ferromagnetic ordering with moment perpendicular to the c axis below 7 K. Heat capacity data show little evidence of heavy fermion behavior. Resistivity measurements show that both LaNi0.35Ga3.65 and CeNi0.74Ga3.26 exhibit metallic behavior. Density of states calculations support this and indicate that Ni/Ga mixing in the compound stabilizes the structure.

An1.33T4Al8Si2 (An = Ce, Th, U, Np; T = Ni, Co): Actinide Intermetallics with Disordered Gd1+xFe4Si10-y Structure Type Grown from Metal Flux.

An1.33T4Al8Si2 (An = Ce, Th, U, Np; T = Ni, Co) were synthesized in metal flux reactions carried out in aluminum/gallium melts. In previous work, U1.33T4Al8Si2 (T = Co, Ni) analogues were formed by arc-melting U:T:Si and reacting this mixture in Al/Ga flux. However, in the current work, all compounds were synthesized by using AnO2 reactants, taking advantage of the ability of the aluminum in the flux to act as both solvent and reducing agent. While reactions with T = Co yielded hexagonal Gd1.33Fe4Si10-type quaternary phases for all An, reactions with T = Ni produced these compounds only with An = U and Np. For reactions with An = Ce and Th, the reactions led instead to the formation of AnNi3-xSixAl4-yGay phases, with the tetragonal KCu3S4 structure type. Attempts to synthesize plutonium analogues Pu1.33T4Al8Si2 were also unsuccessful, producing the previously reported PuCoGa5 and Pu2Ni5Si6 instead. Magnetic data collected on the neptunium analogues Np1.33T4Al8Si2 (T = Ni, Co) show antiferromagnetic coupling at low temperatures and indicate a tetravalent state for the Np ions.

Understanding the Stabilization and Tunability of Divalent Europium 2.2.2B Cryptates.

Lanthanides such as europium with more accessible divalent states are useful for studying redox stability afforded by macrocyclic organic ligands. Substituted cryptands, such as 2.2.2B cryptand, that increase the oxidative stability of divalent europium also provide coordination environments that support synthetic alterations of Eu(II) cryptate complexes. Two single crystal structures were obtained containing nine-coordinate Eu(II) 2.2.2B cryptate complexes that differ by a single coordination site, the occupation of which is dictated by changes in reaction conditions. A crystal structure containing a [Eu(2.2.2B)Cl]+ complex is obtained from a methanol-THF solvent mixture, while a methanol-acetonitrile solvent mixture affords a [Eu(2.2.2B)(CH3OH)]2+ complex. While both crystals exhibit the typical blue emission observed in most Eu(II) containing compounds as a result of 4f65d1 to 4f7 transitions, computational results show that the substitution of a Cl- anion in the place of a methanol molecule causes mixing of the 5d excited states in the Eu(II) 2.2.2B cryptate complex. Additionally, magnetism studies reveal the identity of the capping ligand in the Eu(II) 2.2.2B cryptate complex may also lead to exchange between Eu(II) metal centers facilitated by π-stacking interactions within the structure, slightly altering the anticipated magnetic moment. The synthetic control present in these systems makes them interesting candidates for studying less stable divalent lanthanides and the effects of precise modifications of the electronic structures of low valent lanthanide elements.

Using Redox-Active Ligands to Generate Actinide Ligand Radical Species.

Using a redox-active dioxophenoxazine ligand, DOPO (DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazine-9-olate), a family of actinide (U, Th, Np, and Pu) and Hf tris(ligand) coordination compounds was synthesized. The full characterization of these species using 1H NMR spectroscopy, electronic absorption spectroscopy, SQUID magnetometry, and X-ray crystallography showed that these compounds are analogous and exist in the form M(DOPOq)2(DOPOsq), where two ligands are of the oxidized quinone form (DOPOq) and the third is of the reduced semiquinone (DOPOsq) form. The electronic structures of these complexes were further investigated using CASSCF calculations, which revealed electronic structures consistent with metals in the +4 formal oxidation state and one unpaired electron localized on one ligand in each complex. Furthermore, f orbitals of the early actinides show a sizable bonding overlap with the ligand 2p orbitals. Notably, this is the first example of a plutonium-ligand radical species and a rare example of magnetic data being recorded for a homogeneous plutonium coordination complex.

Fantastic n = 4: Ce5Co4+xGe13-ySny of the An+1MnX3n+1 homologous series.

Ce-based intermetallics are of interest due to the potential to study the interplay of localized magnetic moments and conduction electrons. Our work on Ce-based germanides led to the identification of a new homologous series An+1MnX3n+1 (A = rare earth, M = transition metal, X = tetrels, and n = 1-6). This work presents the single-crystal growth, structure determination, and anisotropic magnetic properties of the n = 4 member of the Cen+1ConGe3n+1 homologous series. Ce5Co4+xGe13-ySny consists of three Ce sites, three Co sites, seven Ge sites, and two Sn sites, and the crystal structure is best modeled in the orthorhombic space group Cmmm where a = 4.3031(8) Å, b = 45.608(13) Å, and c = 4.3264(8) Å, which is in close agreement with the previously reported Sn-free analog where a = 4.265(1) Å, b = 45.175(9) Å, and c = 4.293(3) Å. Anisotropic magnetic measurements show Kondo-like behavior and three magnetic transitions at 6, 4.9, and 2.4 K for Ce5Co4+xGe13-ySny.

Structural Disorder in Intermetallic Boride Pr21M16Te6B30 (M = Mn, Fe): A Transition Metal Cluster and Its Evil Twin.

Reactions of boron, tellurium, and either iron or manganese in a praseodymium-nickel flux led to the production of Pr21M16Te6B30 (M = Fe or Mn) with a novel structure type that features M16B30 clusters surrounded by a Pr/Te framework. Due to disorder in the orientation of the transition metal boride clusters, these phases initially appear to form in the cubic space group Pm3̅m. However, analysis of site occupancy, bond lengths, and local structure in the M16B30 sublattice indicates the local symmetry is P4̅3m. This space group symmetry is supported by transmission electron microscopy studies including selected area electron diffraction (SAED) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), which indicate ordered regions. The M16B30 cluster twinning domain that could be as small as nanometer size inside a single crystal results in the misleading Pm3̅m symmetry. Electronic structure calculations indicate the Pr21M16Te6B30 phases are metals. Magnetic susceptibility measurements show that both the praseodymium and the transition metal have magnetic moments in these compounds. Pr21Mn16Te6B30 exhibits antiferromagnetic ordering at TN = 15 K, and Pr21Fe16Te6B30 undergoes a likely ferrimagnetic transition at TC = 23 K.

Flux Synthesis of MgNi2Bi4 and Its Structural Relationship to NiBi3.

MgNi2Bi4 was grown from the reaction of magnesium and nickel in excess bismuth flux. It forms as large, malleable crystals with a new structure type in orthorhombic space group Cmcm. The structure contains a building block common to Ni-Bi binary phases-nickel zigzag chains running along one direction and surrounded by bismuth. Magnetic susceptibility and transport measurements indicate that the compound is metallic; this is supported by calculations of density of states. Crystal orbital Hamilton population analyses indicate that Ni-Bi interactions are the strongest bonding interactions in the structure, whereas Bi-Bi bonding between the layers is negligible, making MgNi2Bi4 a potential two-dimensional material.

Employing Lewis Acidity to Generate Bimetallic Lanthanide Complexes.

With the advent of lanthanide-based technologies, there is a clear need to advance the fundamental understanding of 4f-element chelation chemistry. Herein, we contribute to a growing body of lanthanide chelation chemistry and report the synthesis of bimetallic 4f-element complexes within an imine/hemiacetalate framework, Ln2TPTOMe [Ln = lanthanide; TPTOMe = tris(pyridineimine)(Tren)tris(methoxyhemiacetalate); Tren = tris(2-aminoethylamine)]. These products are generated from hydrolysis and methanolysis of the cage ligand tris(pyridinediimine)bis(Tren) (TPT; Tadanobu et al. Chem. Lett. 1993, 22 (5), 859-862) likely facilitated by inductive effects stemming from the Lewis acidic lanthanide cations. These complexes are interesting because they result from imine cleavage to generate two metal binding sites: one pocketed site within the macrocycle and the other terminal site capping a hemiacetalate moiety. A clear demarcation in reactivity is observed between samarium and europium, where the lighter and larger lanthanides generate a mixture of products, Ln2TPTOMe and LnTPT. Meanwhile, the heavier and smaller lanthanides generate exclusively bimetallic Ln2TPTOMe. The cleavage reactivity to form Ln2TPTOMe was extended beyond methanol to include other primary alcohols.

Structural, Electronic, and Thermal Properties of CdSnAs2.

Structural, electrical, and thermal properties of CdSnAs2, with analyses from temperature-dependent transport properties over a large temperature range, are reported. Phase-pure microcrystalline powders were synthesized that were subsequently densified to a high-density homogeneous polycrystalline specimen for this study. Temperature-dependent transport indicates n-type semiconducting behavior with a very high and nearly temperature independent mobility over the entire measured temperature range, attributed to the very small electron effective mass of this material. The Debye model was successfully applied to model the thermal conductivity and specific heat. This work contributes to the fundamental understanding of this material, providing further insight and allowing for investigations into altering this and related physical properties of these materials for technological applications.

Phase diagram of URu2-x Fe x Si2 in high magnetic fields.

Electrical transport measurements were performed on URu2 - x Fe x Si2 single-crystal specimens in high magnetic fields up to 45 T (DC fields) and 60 T (pulsed fields). We observed a systematic evolution of the critical fields for both the hidden-order (HO) and large-moment antiferromagnetic (LMAFM) phases and established the 3D phase diagram of T-H-x In the HO phase, H/H0 scales with T/T0 and collapses onto a single curve. However, in the LMAFM phase, this single scaling relation is not satisfied. Within a certain range of x values, the HO phase reenters after the LMAFM phase is suppressed by the magnetic field, similar to the behavior observed for URu2Si2 within a certain range of pressures.

U1.33T4Al8Si2 (T = Ni, Co): Complex Uranium Silicides Grown from Aluminum/Gallium Flux Mixtures.

Two new quaternary analogs of the Gd1+xFe4Si10-y structure type were grown from the reaction of uranium, silicon, and a transition metal (nickel or cobalt) in an excess of aluminum/gallium flux. The use of a mixed flux was found to be necessary for the formation of U1.33T4Al8Si2 (T = Ni, Co). Single crystal X-ray diffraction data shows the presence of disordered U/Si layers that are characteristic of this structure type; precession photographs indicate partial formation of a superstructure and stacking disorder along the c-axis. This disorder may be the cause of the spin glass behavior that is particularly evident in the nickel analog, which exhibits a spin freezing transition at TF = 7 K. These compounds are resistant to chemical attack and oxidation and may be potential waste forms.

Electronic, Magnetic, and Theoretical Characterization of (NH4)4UF8, a Simple Molecular Uranium(IV) Fluoride.

The simple system of tetraammonium octafluorouranate is employed to derive a fundamental understanding of the uranium-fluorine interaction. The structure is composed of isolated molecules, enabling a detailed examination of the U4+ ( f2) ion. Characterization of single-crystals by X-ray diffraction, absorption spectroscopy, and magnetic analysis up to 45 T is combined with extensive theoretical treatment by CASSCF. The influence of different active spaces and representations of the structure is examined in the context of the experimental evidence. The Interacting Quantum Atoms method (IQA) is used to examine the nature of the U-F bond, concluding that there is a non-negligible degree of covalent character (9% of the total bond energy) in [UF8]4-. For the structural and theoretical reasons discussed herein, it is proposed that the structure of (NH4)4UF8 may be appropriately employed as a benchmark compound for future theoretical characterization of U(IV).

Uncovering the Origin of Divergence in the CsM(CrO4)2 (M = La, Pr, Nd, Sm, Eu; Am) Family through Examination of the Chemical Bonding in a Molecular Cluster and by Band Structure Analysis.

A series of f-block chromates, CsM(CrO4)2 (M = La, Pr, Nd, Sm, Eu; Am), were prepared revealing notable differences between the AmIII derivatives and their lanthanide analogs. While all compounds form similar layered structures, the americium compound exhibits polymorphism and adopts both a structure isomorphous with the early lanthanides as well as one that possesses lower symmetry. Both polymorphs are dark red and possess band gaps that are smaller than the LnIII compounds. In order to probe the origin of these differences, the electronic structure of α-CsSm(CrO4)2, α-CsEu(CrO4)2, and α-CsAm(CrO4)2 were studied using both a molecular cluster approach featuring hybrid density functional theory and QTAIM analysis and by the periodic LDA+GA and LDA+DMFT methods. Notably, the covalent contributions to bonding by the f orbitals were found to be more than twice as large in the AmIII chromate than in the SmIII and EuIII compounds, and even larger in magnitude than the Am-5f spin-orbit splitting in this system. Our analysis indicates also that the Am-O covalency in α-CsAm(CrO4)2 is driven by the degeneracy of the 5f and 2p orbitals, and not by orbital overlap.

Visualizing heavy fermions emerging in a quantum critical Kondo lattice.

In solids containing elements with f orbitals, the interaction between f-electron spins and those of itinerant electrons leads to the development of low-energy fermionic excitations with a heavy effective mass. These excitations are fundamental to the appearance of unconventional superconductivity and non-Fermi-liquid behaviour observed in actinide- and lanthanide-based compounds. Here we use spectroscopic mapping with the scanning tunnelling microscope to detect the emergence of heavy excitations with lowering of temperature in a prototypical family of cerium-based heavy-fermion compounds. We demonstrate the sensitivity of the tunnelling process to the composite nature of these heavy quasiparticles, which arises from quantum entanglement of itinerant conduction and f electrons. Scattering and interference of the composite quasiparticles is used to resolve their energy-momentum structure and to extract their mass enhancement, which develops with decreasing temperature. The lifetime of the emergent heavy quasiparticles reveals signatures of enhanced scattering and their spectral lineshape shows evidence of energy-temperature scaling. These findings demonstrate that proximity to a quantum critical point results in critical damping of the emergent heavy excitation of our Kondo lattice system.