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DOE OSTI2014

The molten hydrated flux synthesis of a novel open-framework copper borophosphate and its structural relation with the precursors

A novel copper borophosphate, Cu{sub 2}(H{sub 2}O)[BP{sub 2}O{sub 7}(OH)], has been synthesized by the molten hydrated flux method. Its crystal structure (Orthorhombic, Pbca, a=8.234 Å, b=9.655 Å, c=17.805 Å, V=1415.485 Å{sup 3}, Z=8) can be regarded as the condensation of alternately edge- and corner-shared copper pyramidal chains and borophosphate chains formed via vertex-sharing PO{sub 4} and BO{sub 3}(OH) tetrahedra. Magnetic measurements indicate that antiferromagnetic interactions exist in the title compound. Due to the special reaction medium created by the molten hydrated flux method, a possible structural correlation between final solids and raw materials has been discovered even though no ordered structural fragments exist in the latter. - Graphical: Structure comparison of Cu(NO{sub 3}){sub 2}·3H{sub 2}O, Cu(NO{sub 3}){sub 2}·H{sub 2}O and Cu{sub 2}(H{sub 2}O)[BP{sub 2}O{sub 7}(OH)], showing the structural evolution of CuO{sub 5} pyramids in the synthetic process. - Highlights: • A novel copper borophosphate has been synthesized by the molten hydrated flux method. • Magnetic measurements show its antiferromagnetism at low temperature. • A structural relation between the precursor and the final solid is discovered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Syntheses, structures and magnetic properties of four coordination polymers based on nitrobenzene dicarboxylate and various N-donor coligands

Four new coordination polymers ([Ni(4-Nbdc)(bpa)(H{sub 2}O)]){sub n} (1), ([Co(4-Nbdc)(bpp) (H{sub 2}O)]){sub n} (2), ([Ni(4-Nbdc)(bpp)(H{sub 2}O)]·H{sub 2}O){sub n} (3), and ([Mn{sub 2}(3-Nbdc){sub 2}(bib){sub 3}]·2H{sub 2}O){sub n} (4) (4-Nbdc=4-nitrobenzene-1,2-dicarboxylate, 3-Nbdc=3-nitrobenzene-1,2-dicarboxylate, bpa=1,2-bi(4-pyridyl)ethane, bpp=1,3-bis(4-pyridyl)propane, and bib=1,4-bis(1-imidazoly)benzene), were synthesized by hydrothermal reactions, and characterized by single-crystal X-ray diffractions, elemental analysis, FT-IR, PXRD, TGA and magnetic analysis. Complexes 1 and 2 display quasi-trapezoidal chain and brick-wall layer, and both of them contain metal–carboxylate binuclear units. Complexes 3 and 4 exhibit three-dimensional frameworks with the (6{sup 6}) dia topology and (4{sup 4}.6{sup 10}.8)(4{sup 4}.6{sup 2}) fsc topology, and both of them contain metal–carboxylate chains. The carboxyl groups with syn-anti coordination mode mediate effectively the weak ferromagnetic coupling interaction within Ni(II)–carboxylate binuclear in 1 (J=1.27 cm{sup −1}) and Ni(II)–carboxylate chain in 3 (J=1.44 cm{sup −1}), respectively, and the carboxyl groups with anti-anti coordination mode leads to the classic antiferromagnetic coupling interaction within Mn(II)–carboxylate chain in 4 (J=−0.77 cm{sup −1}). - Highlights: • Four novel coordination polymers were hydrothermally synthesized. • 1 is 1D quasi-trapezoidal chain and 2 is brick-wall layer both with dinuclear units. • 3 and 4 show 3D frameworks both with 1D metal–carboxylate chains. • 1 and 3 exhibit ferromagnetic coupling, while 4 shows antiferromagnetic coupling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Synthesis, structure and properties of layered iron-oxychalcogenides Nd{sub 2}Fe{sub 2}Se{sub 2−x}S{sub x}O{sub 3}

A new series of sulfur-substituted iron-oxychalcogenides Nd{sub 2}Fe{sub 2}Se{sub 2−x}S{sub x}O{sub 3} (0≤x≤0.4) was synthesized by solid state reaction method, and investigated by structure, transport, magnetic and specific heat measurements. The compounds crystallize in the layered tetragonal structure with I4/mmm space group, and show semiconducting behavior. The large discrepancy between the activation energies for conductivity, E{sub ρ} (152–202 meV), and thermopower, E{sub S} (15.6–39.8 meV), indicates the polaronic transport mechanism of the carrier. The parent compound Nd{sub 2}Fe{sub 2}Se{sub 2}O{sub 3} exhibits a frustrated antiferromagnetic (AFM) ground state, and the S-substitution induces an enhanced ferromagnetic (FM) component and possible increased degree of frustration. - Graphical abstract: The crystal structure of Nd{sub 2}Nd{sub 2}Fe{sub 2}Se{sub 2−x}S{sub x}O{sub 3} is built up by stacking fluorite-like Nd{sub 2}O{sub 2} layers and anti-CuO{sub 2}-type Fe{sub 2}O(Se/S){sub 2} layers with Fe{sup 2+} cations coordinated by two in-plane O{sup 2-} and four Se{sup 2-} above and below the square Fe{sub 2}O plane. - Highlights: • We have synthesized a new series of layered iron-oxychalcogenides Nd{sub 2}Fe{sub 2}Se{sub 2−x}S{sub x}O{sub 3}. • They crystallize in layered tetragonal structure and show semiconducting behavior. • The transport analysis indicates the polaronic transport mechanism of the carrier. • The parent compound shows a frustrated antiferromagnetic (AFM) ground state. • The S-substitution induces an enhanced ferromagnetic (FM) component.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

The U{sup 5+} compound Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24}: Synthesis, structure, and electronic properties

Black crystals of Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24} have been made by direct combination of BaS, Ag, U, and S at 1273 K. This compound crystallizes in a new structure type in the space group C{sub 4v}{sup 10}−I4cm of the tetragonal system with four formula units in a cell with lattice constants a=13.9189(6) Å and c=23.7641(11) Å (V=4604(5) Å{sup 3}). Multiphoton Luminescence Spectroscopy measurements are consistent with the noncentrosymmetric nature of the structure. In the structure each U atom is octahedrally coordinated by six S atoms, whereas three of the five crystallographically independent Ag atoms are tetrahedrally coordinated to four S atoms, another has a seesaw coordination to four S atoms, and the last has a triangular coordination to three S atoms. The overall structure consists of the three-dimensional stacking of the US{sub 6}, AgS{sub 4}, and AgS{sub 3} polyhedra to leave channels in which Ba atoms reside. Based on the values of the U–S interatomic distances, the compound Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24} contains U{sup 5+} and charge balance is achieved with the formal oxidation states of 9 Ba{sup 2+}, 10 Ag{sup 1+}, 4 U{sup 5+} and 24 S{sup 2−}. DFT calculations predict an antiferromagnetic ground state and a band gap of 2.1 eV. Resistivity measurements indicate that the compound is a semiconductor with a complex activation mechanism and activation energies ranging from 0.03(1) eV to 0.08(1) eV. - Graphical abstract: General view of the Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24} structure. - Highlights: • Black crystals of Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24} have been made by direct combination of BaS, Ag, U, and S at 1273 K. • Ba{sub 9}Ag{sub 10}U{sub 4}S{sub 24} contains U{sup 5+} and charge balance is achieved with 9 Ba{sup 2+}, 10 Ag{sup 1+}, 4 U{sup 5+}, and 24 S{sup 2−}. • DFT calculations predict an antiferromagnetic ground state and a band gap of 2.1 eV. • The compound is a semiconductor with activation energies ranging from 0.03(1) eV to 0.08(1) eV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

The Ho–Ni–Ge system: Isothermal section and new rare-earth nickel germanides

The Ho–Ni–Ge system has been investigated at 1070 K and up to ~60 at% Ho by X-ray diffraction and microprobe analyses. Besides the eight known compounds, HoNi{sub 5}Ge{sub 3} (YNi{sub 5}Si{sub 3}-type), HoNi{sub 2}Ge{sub 2} (CeAl{sub 2}Ga{sub 2}-type), Ho{sub 2}NiGe{sub 6} (Ce{sub 2}CuGe{sub 6}-type), HoNiGe{sub 3} (SmNiGe{sub 3}-type), HoNi{sub 0.2÷0.6}Ge{sub 2} (CeNiSi{sub 2}-type), Ho{sub 37÷34}Ni{sub 6÷24}Ge{sub 57÷42} (AlB{sub 2}-type), HoNiGe (TiNiSi-type), Ho{sub 3}NiGe{sub 2} (La{sub 3}NiGe{sub 2}-type), the ternary system contains four new compounds: Ho{sub 3}Ni{sub 11}Ge{sub 4} (Sc{sub 3}Ni{sub 11}Ge{sub 4}-type), HoNi{sub 3}Ge{sub 2} (ErNi{sub 3}Ge{sub 2}-type), Ho{sub 3}Ni{sub 2}Ge{sub 3} (Hf{sub 3}Ni{sub 2}Si{sub 3}-type) and ~Ho{sub 5}Ni{sub 2}Ge{sub 3} (unknown structure). Quasi-binary solid solutions were observed at 1070 K for Ho{sub 2}Ni{sub 17}, HoNi{sub 5}, HoNi{sub 7}, HoNi{sub 3}, HoNi{sub 2}, HoNi and Ho{sub 2}Ge{sub 3}, but no detectable solubility was found for the other binary compounds in the Ho–Ni–Ge system. Based on the magnetization measurements, the HoNi{sub 5}Ge{sub 3}, HoNi{sub 3}Ge{sub 2} and Ho{sub 3}Ni{sub 11}Ge{sub 4} (and isostructural (Tb, Dy){sub 3}Ni{sub 11}Ge{sub 4}) compounds have been found to show paramagnetic behavior down to 5 K, whereas Ho{sub 3}Ni{sub 2}Ge{sub 3} exhibits an antiferromagnetic transition at ~7 K. Additionally, the crystal structure of the new isostructural phases (Y, Yb)Ni{sub 3}Ge{sub 2} (ErNi{sub 3}Ge{sub 2}-type), Er{sub 3}Ni{sub 11}Ge{sub 4} (Sc{sub 3}Ni{sub 11}Ge{sub 4}-type) and (Y, Tb, Dy, Er, Tm){sub 3}Ni{sub 2}Ge{sub 3} (Hf{sub 3}Ni{sub 2}Si{sub 3}-type) has been also investigated. - Graphical abstract: The Ho–Ni–Ge system has been investigated at 1070 K and up to ~60 at.% Ho by X-ray and microprobe analyses. Besides the eight known compounds, i.e. HoNi{sub 5}Ge{sub 3} (YNi{sub 5}Si{sub 3}-type), HoNi{sub 2}Ge{sub 2} (CeAl{sub 2}Ga{sub 2}-type), Ho{sub 2}NiGe{sub 6} (Ce{sub 2}CuGe{sub 6}-type), HoNiGe{sub 3} (SmNiGe{sub 3}-type), HoNi{sub 0.2÷0.6}Ge{sub 2} (CeNiSi{sub 2}-type), Ho{sub 37÷34}Ni{sub 6÷24}Ge{sub 57÷42} (AlB{sub 2}-type), HoNiGe (TiNiSi-type), Ho{sub 3}NiGe{sub 2} (La{sub 3}NiGe{sub 2}-type), the ternary system contains four new compounds: Ho{sub 3}Ni{sub 11}Ge{sub 4} (Sc{sub 3}Ni{sub 11}Ge{sub 4}-type), HoNi{sub 3}Ge{sub 2} (ErNi{sub 3}Ge{sub 2}-type), Ho{sub 3}Ni{sub 2}Ge{sub 3} (Hf{sub 3}Ni{sub 2}Si{sub 3}-type) and ~Ho{sub 5}Ni{sub 2}Ge{sub 3} (unknown structure). Quasi-binary solid solutions were found to form at 1070 K from the binary Ho{sub 2}Ni{sub 17}, HoNi{sub 5}, HoNi{sub 7}, HoNi{sub 3}, HoNi{sub 2}, HoNi and Ho{sub 2}Ge{sub 3} compounds, while no detectable solubility was observed for the other binary compounds in the Ho–Ni–Ge system. Based on the magnetization measurements, the HoNi{sub 5}Ge{sub 3}, HoNi{sub 3}Ge{sub 2} and Ho{sub 3}Ni{sub 11}Ge{sub 4} (and isostructural (Tb, Dy){sub 3}Ni{sub 11}Ge{sub 4}) compounds have been found to show paramagnetic behavior down to 5 K, whereas Ho{sub 3}Ni{sub 2}Ge{sub 3} exhibits an antiferromagnetic transition at ~7 K. Additionally, the crystal structure of the new isostructural phases (Y, Yb)Ni{sub 3}Ge{sub 2} (ErNi{sub 3}Ge{sub 2}-type), Er{sub 3}Ni{sub 11}Ge{sub 4} (Sc{sub 3}Ni{sub 11}Ge{sub 4}-type) and (Y, Tb, Dy, Er, Tm){sub 3}Ni{sub 2}Ge{sub 3} (Hf{sub 3}Ni{sub 2}Si{sub 3}-type) has been also investigated. - Highlights: • Ho–Ni–Ge system has been investigated at 1070 K and up to ~60 at% Ho. • Eight known ternary holmium nickel germanides were confirmed in Ho–Ni–Ge. • Four new holmium nickel germanides were detected in Ho–Ni–Ge. • Eight new rare earth nickel germanides were detected in (Y, Tb, Dy, Er–Yb)–Ni–Ge. • HoNi{sub 5}Ge{sub 3}, HoNi{sub 3}Ge{sub 2},(Tb, Dy, Ho){sub 3}Ni{sub 11}Ge{sub 4} and Ho{sub 3}Ni{sub 2}Ge{sub 3} are paramagnet down to 5–7 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

The Bi{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}–Sb{sub 2}O{sub 5} system phase diagram refinement, Bi{sub 3}FeSb{sub 2}O{sub 11} structure peculiarities and magnetic properties

The refinement of the Bi{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}–Sb{sub 2}O{sub 5} system phase diagram has been performed and the existence of the two ternary compounds has been confirmed. The first one with a pyrochlore-type structure (sp. gr. Fd 3-barm) exists in the wide solid solution region, (Bi{sub 2−x}Fe{sub x})Fe{sub 1+y}Sb{sub 1−y}O{sub 7±δ}, where x=0.1–0.4 and y=−0.13–0.11. The second one, Bi{sub 3}FeSb{sub 2}O{sub 11}, corresponds to the cubic KSbO{sub 3}-type structure (sp. gr. Pn 3-bar) with unit cell parameter a=9.51521(2) Å. The Rietveld structure refinement showed that this compound is characterized by disordered structure. The Bi{sub 3}FeSb{sub 2}O{sub 11} factor group analysis has been carried out and a Raman spectrum has been investigated. According to magnetization measurements performed at the temperature range 2–300 K it may be concluded that the Bi{sub 3}FeSb{sub 2}O{sub 11} magnetic properties can be substantially described as a superposition of strong short-range antiferromagnetic exchange interactions realizing inside the [(FeSb{sub 2})O{sub 9}] 3D-framework via different pathways. - Graphical abstract: The refinement of the Bi{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}–Sb{sub 2}O{sub 5} system phase diagram has been performed and the existence of the solid solution with a pyrochlore-type structure (sp. gr. Fd 3-barm) and Bi{sub 3}FeSb{sub 2}O{sub 11}, correspond of the cubic KSbO{sub 3}-type structure (sp. gr. Pn 3-bar has been confirmed. The structure refinement, Raman spectroscopy as well as magnetic measurements data of Bi{sub 3}FeSb{sub 2}O{sub 11} are presented. - Highlights: • The Bi{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}–Sb{sub 2}O{sub 5} system phase diagram refinement has been performed. • The Bi{sub 3}FeSb{sub 2}O{sub 11} existence along with pyrochlore structure compound is shown. • It was determined that the Bi{sub 3}FeSb{sub 2}O{sub 11} is of disordered cubic KSbO{sub 3}-type structure. • Factor group analysis of Bi{sub 3}FeSb{sub 2}O{sub 11} vibrational spectrum has been performed. • Short-range antiferromagnetic interactions govern Bi{sub 3}FeSb{sub 2}O{sub 11} magnetic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Syntheses, crystal structures, and properties of new metal-5-bromonicotinate coordination polymers

Four metal–5-bromonicotinate (Brnic) coordination polymers [Fe(Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (1), [Ni(Brnic){sub 2}]{sub n} (2), [Ni(Brnic)(bpy)(H{sub 2}O){sub 2}]{sub n}·n(Brnic)·4.5nH{sub 2}O (3), and [Co{sub 2}(Brnic){sub 3}(bpy){sub 2}(OH)]{sub n}·nH{sub 2}O (4) have been synthesized and structurally characterized (bpy=4,4′-bipyridine). Complex 1 has corrugated (4,4) sheets formed by μ-Brnic ligands and planar nodes Fe(II). As for 2–4, they all built up from Brnic-bridged dinuclear subunits, but have very different structure features. Complex 2 is a twin-like polymer with (4,4) layers formed by twin paddle-wheel [Ni{sub 2}(Brnic){sub 4}] subunits. Through the bridge coordination of bpy ligands with dinuclear rings [Ni{sub 2}(Brnic){sub 2}] and trigons [Co{sub 2}(Brnic){sub 3}(OH)], 6{sup 3}-topological cationic layers with nanosized grids of 3 and chiral ladder-type double chains of 4 formed, respectively. Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules 1–4. The thermostabilities of all compounds have been discussed in detail. Moreover, the magnetic investigations of 2 and 4 indicate that there exist antiferromagnetic interactions in the paddle-wheel [Ni{sub 2}(Brnic){sub 4}] and trigon [Co{sub 2}(Brnic){sub 3}(OH)] cores, respectively. - Highlights: • Four novel metal–5-bromonicotinate coordination polymers have been synthesized. • Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules. • Antiferromagnetic interactions in nickel(II) paddle-wheel and cobalt(II) trigon cores were observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Structural and electronic properties of Li-ion battery cathode material MoF{sub 3} from first-principles

The transition metal fluorides have been extensively investigated recently as the electrode materials with high working voltage and large capacity. The structural, electronic and magnetic properties of MoF{sub 3} are studied by the first-principles calculations within both the generalized gradient approximation (GGA) and GGA+U frameworks. Our results show that the antiferromagnetic configuration of MoF{sub 3} is more stable than the ferromagnetic one, which is consistent with experimental results. The analysis of the electronic density of states shows that MoF{sub 3} is a Mott–Hubbard insulator with a d–d type band gap, which is similar to the case of FeF{sub 3}. Moreover, small spin polarizations were found on the sites of fluorine ions, which accords with a fluorine-mediated superexchange mechanism for the Mo–Mo magnetic interaction. - Graphical abstract: Deformation charge density and spin-density for MoF{sub 3} in the AF configuration. - Highlights: • The ground state of MoF{sub 3} is shown to be antiferromagnetic, in consistent with experiments. • The electronic states show that MoF{sub 3} is a Mott–Hubbard insulator with a d–d type band gap. • A fluorine-mediated super-exchange mechanism for the Mo–Mo magnetic interaction is shown.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2015

A family of rare earth molybdenum bronzes: Oxides consisting of periodic arrays of interacting magnetic units

The family of rare earth molybdenum bronzes, reduced ternary molybdates of composition LnMo{sub 16}O{sub 44,} was synthesized and a detailed structural study carried out. Bond valence sum (BVS) calculations clearly show that the molybdenum ions in tetrahedral coordination are hexavalent while the electron count in the primitive unit cell is odd. Yet, measurements show that the phases are semiconductors. The temperature dependence of the magnetic susceptibility of samples containing several different rare earth elements was measured. These measurements verified the presence of a 6.5 K magnetic phase transition not arising from the rare earth constituent, but likely associated with the unique isolated ReO{sub 3}-type Mo{sub 8}O{sub 36} structural subunits in this phase. To better understand the behavior of these materials, electronic structure calculations were performed within density functional theory. Results suggest a magnetic state in which these structural moieties have an internal ferromagnetic arrangement, with small ~1/8 μ{sub B} moments on each Mo. We suggest that the Mo{sub 8}O{sub 36} units behave like pseudoatoms with spin 1/2 derived from a single hole distributed over the eight Mo atoms that are strongly hybridized with the O atoms of the subunit. Interestingly, while the compound is antiferromagnetic, our calculations suggest that a field-stabilized ferromagnetic state, if achievable, will be a narrow band half-metal. - Graphical abstract: LnMo{sub 16}O{sub 44} phases comprise corner sharing tetrahedral and octahedral molybdenum ions. The MoO{sub 6} octahedra form Mo{sub 8}O{sub 36} units that are well separated and act like pseudo-atoms, accommodating 11 electrons each. - Highlights: • Single crystal X-ray diffraction refinements of LnMo{sub 16}O{sub 44} single crystals for Ln=Ce, Pr, Nd, Tb, Dy and Ho. • DFT calculations based on LaMo{sub 16}O{sub 44}. • [Mo{sub 8}O{sub 36}] units behaving as superatoms with a net magnetic moment of 1 µ{sub B}. • Bronze structure containing equal number of molybdenum tetrahedra and octahedral.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Syntheses, structure and magnetic properties of two vanadate garnets Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni)

Two vanadate compounds Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) have been synthesized by a high-temperature solid-state reaction. The compounds are found to crystallize in the cubic system with a space group Ia-3d, which exhibit a typical garnet structural framework. Magnetic measurements show that Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) exhibit similar magnetic behaviors, in which Ca{sub 5}Co{sub 4}V{sub 6}O{sub 24} possesses an antiferromagnetic ordering at T{sub N}=~6 K while Ca{sub 5}Ni{sub 4}V{sub 6}O{sub 24} shows an antiferromagnetic ordering at T{sub N}=~7 K. - Graphical abstract: Garnet vanadate compounds Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) have been synthesized by a high-temperature solid-state reaction. Structural features and magnetic behaviors are also investigated. - Highlights: • New type of garnet vanadates Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) are synthesized by a high-temperature solid-state reaction. • Structural features are confirmed by single crystal samples. • Magnetic behaviors are firstly investigated in the systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

RFe{sub 2}Mg{sub x}Al{sub 8−x} (R=La–Nd and Sm; x≈0.8): Flux synthesis, structure, magnetic and electrical properties

Single crystals of Mg-substituted CeFe{sub 2}Al{sub 8} type intermetallics RFe{sub 2}Mg{sub x}Al{sub 8–x} (R=La–Nd and Sm; x≤1) were grown by reacting iron and rare earth metals in 1:1 Mg/Al mixed flux. The structure features mono-capped and bi-capped trigonal prismatic FeAl{sub 6} units. Electronic structure calculations indicate that magnesium substitution reduces the valence electron count, shifting the Fermi level away from a pseudo-gap. This changes the electronic nature of the cerium analog; the previously reported ternary CeFe{sub 2}Al{sub 8} shows strong hybridization between the cerium states and the conduction electrons, resulting in no magnetic moment on Ce atoms. On the other hand, magnetic susceptibility measurements on CeFe{sub 2}Mg{sub x}Al{sub 8–x} indicates a localized moment on cerium. The newly synthesized Pr, Nd and Sm analogs exhibit antiferromagnetic ordering at 2.8 K, 7.8 K and 12 K respectively. Solid state {sup 27}Al NMR of LaFe{sub 2}Mg{sub x}Al{sub 8–x} exhibits a broad Knight shift at ~1200 ppm, consistent with the metallic behavior shown by electrical resistivity data. - Graphical abstract: Mg substitution into CeFe{sub 2}Al{sub 8} modifies cerium valence due to changing valence electron count. - Highlights: • RFe{sub 2}Mg{sub x}Al{sub 8−x} (R=La–Nd, Sm) grow as large crystals from reactions in Mg/Al flux. • Products are magnesium-substituted variants of CeFe{sub 2}Al{sub 8}, with CaCo{sub 2}Al{sub 8} structure. • Ce magnetic moment in CeFe{sub 2}Mg{sub x}Al{sub 8−x} varies from that in CeFe{sub 2}Al{sub 8} due to VEC change. • Antiferromagnetic ordering observed for Pr, Nd, Sm analogs of RFe{sub 2}Mg{sub x}Al{sub 8−x}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Structure and physical properties of RE{sub 2}AgGe{sub 3} (RE=Ce, Pr, Nd) compounds

We have synthesized the compounds RE{sub 2}AgGe{sub 3} (RE =Ce, Pr, Nd) by arc melting. The crystal structure obtained from single crystal and powder X-ray diffraction suggests that these compounds crystallize in the α-ThSi{sub 2} structure type. The magnetic susceptibility data of Ce{sub 2}AgGe{sub 3} follows Curie–Weiss (CW) law above 25 K without any magnetic ordering down to 2 K. The effective magnetic moment (μ{sub eff}) was calculated as 2.53 μ{sub B}/Ce and negative Curie paramagnetic temperature (θ{sub p})=−2.4 K hint weak antiferromagnetic coupling among the adjacent spins. Pr{sub 2}AgGe{sub 3} shows a complex magnetic behavior wherein the magnetic susceptibility at field cooled and zero field cooled modes bifurcates at 11.5 K with the latter undergoing a cusp like maxima, probably due to weak ferromagnetic interaction. The θ{sub p} and μ{sub eff} obtained are 4 K and 4.33 μ{sub B}/Pr, respectively. Nd{sub 2}AgGe{sub 3} undergoes multiple magnetic transitions. Temperature dependent resistivity data reveals that three compounds are metallic in nature. - Graphical abstract: The compounds Ce{sub 2}AgGe{sub 3}, Pr{sub 2}AgGe{sub 3} and Nd{sub 2}AgGe{sub 3} have been synthesized by arc melting. X-ray diffraction suggests tetragonal α-ThSi{sub 2} type structure and diverse magnetic properties exhibited in the magnetic measurements. - Highlights: • Two new compounds Ce{sub 2}AgGe{sub 3}, Nd{sub 2}AgGe{sub 3} and known Pr{sub 2}AgGe{sub 3} synthesized by arc melting. • Crystal structure of the compounds derived from X-ray diffraction. • Ce{sub 2}AgGe{sub 3} and Pr{sub 2}AgGe{sub 3} exhibit antiferromagnetic ordering. • Nd{sub 2}AgGe{sub 3} shows multiple magnetic transition with ferrimagnetic like behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

A 3D chiral metal-organic framework based on left-handed helices containing 3-amino-1 H-1,2,4-triazole ligand

A chiral metal-organic framework, [Cu(atr)(OH)]·0.5H{sub 2}O·0.5en (1) (Hatr=3-amino-1 H-1,2,4-triazole, en=ethylenediamine), was constructed via diffusion reaction of the achiral Hatr ligand and CuSO{sub 4} as starting materials. Compound 1 crystallizes in the chiral space group P3{sub 2}21 and features a porous metal-organic framework with 44.1% solvent-accessible volume fabricated by left-handed helices with a pitch height of l{sub p}=10.442 Å. Six helices gather around in a cycle forming a large honeycomb channel with a 6.58 Å inner diameter. Cu(II) center and atr{sup ‒} ligand regarded as 3-connected nodes, compound 1 can be simplified to a 3-c uninodal (4.12{sup 2}) (qtz-h) topological network. A gradual decreasing in the magnetic moment depending on temperature decreasing indicates an antiferromagnetic interaction in 1. The powder XRD confirms the bulk sample is a single crystal pure phase, and the thermogravimetric analysis shows the thermal stability of 1 is up to ca. 240 °C. - Highlights: • The present 3D chiral MOF is built from achiral Hatr ligand. • Six left-handed helices gather into a honeycomb channel in chiral sp P3{sub 2}21. • Compound 1 shows a 3-c uninodal (4.12{sup 2}) or qtz-h topological network. • Compound 1 indicates an antiferromagnetic interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Synthesis and anisotropic properties of single crystalline Ln{sub 2}Ru{sub 3}Al{sub 15+x} (Ln=Gd, Tb)

Single crystals of Ln{sub 2}Ru{sub 3}Al{sub 15+x} (Ln=Gd, Tb) have been grown using the self-flux method under Ru-poor conditions. The structure of the Gd analog is found to be highly dependent on the synthesis method. Gd{sub 2}Ru{sub 3}Al{sub 15.08} orders antiferromagnetically at 17.5 K. Tb{sub 2}Ru{sub 3}Al{sub 15.05} enters an antiferromagnetic state at 16.6 K followed by a likely incommensurate-to-commensurate transition at 14.9 K for crystals oriented with H//ab. For crystals oriented with H//c, a broad maximum is observed in the temperature dependent M/H, indicative of a highly anisotropic magnetic system with the hard axis in the c-direction. The magnetization as a function of field and magnetoresistance along the ab-direction of Tb{sub 2}Ru{sub 3}Al{sub 15.05} display a stepwise behavior and indicate strong crystalline electric field effects. - Graphical abstract: Single crystal, structure, and highly anisotropic magnetoresistance due to strong crystalline electric field effects of Tb{sub 2}Ru{sub 3}Al{sub 15.05}. - Highlights: • Single crystals of Ln{sub 2}Ru{sub 3}Al{sub 15+x} were grown for the first time via flux growth. • The structure of Gd{sub 2}Ru{sub 3}Al{sub 15.09} differs from that of arc melted Gd{sub 2}Ru{sub 3.08}Al{sub 15}. • Tb{sub 2}Ru{sub 3}Al{sub 15.05} exhibits highly anisotropic magnetic and transport properties. • The properties of Tb{sub 2}Ru{sub 3}Al{sub 15.05} arise due to crystalline electric field effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Synthesis, crystal structure, and magnetism of A{sub 2}Co{sub 12}As{sub 7} (A=Ca, Y, Ce–Yb)

Ternary intermetallics, A{sub 2}Co{sub 12}As{sub 7} (A=Ca, Y, Ce–Yb), have been synthesized by annealing mixtures of elements in molten Bi at 1223 K. The materials obtained crystallize in the P6{sub 3}/m variant of the Zr{sub 2}Fe{sub 12}P{sub 7} structure type. The unit cell volume shows a monotonic decrease with the increasing atomic number of the rare-earth metal, with the exception of Ce-, Eu-, and Yb-containing compounds. An examination of these outliers with X-ray absorption near edge structures (XANES) spectroscopy revealed mixed valence of Ce, Eu, and Yb, with the average oxidation states of +3.20(1), +2.47(5), and +2.91(1), respectively, at room temperature. Magnetic behavior of A{sub 2}Co{sub 12}As{sub 7} is generally characterized by ferromagnetic ordering of Co 3d moments at 100–140 K, followed by low-temperature ordering of rare-earth 4f moments. The 3d-4f magnetic coupling changes from antiferromagnetic for A=Pr–Sm to ferromagnetic for A=Ce and Eu–Yb. Polarized neutron scattering experiments were performed to support the postulated ferro- and ferrimagnetic ground states for Ce{sub 2}Co{sub 12}As{sub 7} and Nd{sub 2}Co{sub 12}As{sub 7}, respectively. - Graphical abstract: Title arsenides were synthesized by Bi‐flux method. They exhibit mixed valence for A = Ce, Eu, Yb, ferrimagnetism for A = Ca, Y, Pr–Sm, and ferromagnetism for A = Eu–Tm. - Highlights: • A2Co12As7 (A=Ca, Y, Ce–Yb) were synthesized in Bi flux. • Ce, Eu, Yb exhibit mixed valence in the corresponding structures. • The character of 3d‐4f magnetic coupling changes at the half‐filled f shell. • Materials behave as ferrimagnets for A=Ca, Y, Pr–Sm and as ferromagnets for A=Eu–Yb.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Structure and magnetic properties of new Be-substituted langasites A{sub 3}Ga{sub 3}Ge{sub 2}BeO{sub 14} (A=Pr, Nd, and Sm)

Langasites have been studied extensively in past for their functional properties and use in telecommunication. A thorough understanding of their ground state is limited by the difficulty in synthesizing new members belonging to this series due to the formation of competing phases such as the garnets. Three magnetic langasites A{sub 3}Ga{sub 3}Ge{sub 2}BeO{sub 14} (A=Pr, Nd, and Sm) and a non-magnetic lattice standard La{sub 3}Ga{sub 3}Ge{sub 2}BeO{sub 14} were synthesized using the ceramic method. These were further characterized by X-ray diffraction, magnetization, magnetic susceptibility and heat capacity measurements. All three langasites exhibit net antiferromagnetic interactions at low temperatures and no evidence of long range magnetic ordering was observed down to 0.350 K. - Graphical abstract: Kagome network formed by the magnetic ions in the new Be-langasites. The ground states of three new members were explored using different physical property measurements such as X-ray diffraction, magnetization, magnetic susceptibility and heat capacity (a–d show refinement patterns for the langasites). These can be added to the list of candidate spin liquid materials. - Highlights: • Four new langasites A{sub 3}Ga{sub 3}Ge{sub 2}BeO{sub 14} (A=La, Pr, Nd, and Sm) were synthesized. • These were characterized using physical and magnetic property measurements. • These langasites exhibit net antiferromagnetic interactions at low temperatures. • No evidence of long range magnetic ordering was observed down to 0.350 K. • Can be potential Spin liquid candidates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

RNi{sub 8}Si{sub 3} (R=Gd,Tb): Novel ternary ordered derivatives of the BaCd{sub 11} type

The title compounds have been synthesized and characterized both from the structural and magnetic point of view. Both crystallize in a new monoclinic structure strictly related to the tetragonal BaCd{sub 11} type. The structure was solved by means of X-ray single-crystal techniques for GdNi{sub 8}Si{sub 3} and confirmed for TbNi{sub 8}Si{sub 3} on powder data; the corresponding lattice parameters (obtained from Guinier powder patterns) are a=6.3259(2), b=13.7245(5), c=7.4949(3) Å, β=113.522(3)°, V{sub cell}=596.64(3) Å{sup 3} and a=6.3200(2), b=13.6987(4), c=7.4923(2) Å, β=113.494(2)°, V{sub cell}=594.88(2) Å{sup 3}. The symmetry relationship between the tI48-I4{sub 1}/amd BaCd{sub 11} aristotype and the new ordered mS48-C2/c GdNi{sub 8}Si{sub 3} derivative is described via the Bärnighausen formalism within the group theory. The large Gd–Gd (Tb–Tb) distances, mediated via Ni–Si network, likely lead to weak magnetic interactions. Low-field magnetization vs temperature measurements indicate weak and field-sensitive antiferromagnetic ground state, with ordering temperatures of 3 K in GdNi{sub 8}Si{sub 3} and about 2–3 K in TbNi{sub 8}Si{sub 3}. On the other hand, the isothermal field-dependent magnetization data show the presence of competing interactions in both compounds, with a field-induced ferromagnetic behavior for GdNi{sub 8}Si{sub 3} and a ferrimagnetic-like behavior in TbNi{sub 8}Si{sub 3} at the ordering temperature T{sub C/N} of about (or slightly higher than) 3K. The magnetocaloric effect, quantified in terms of isothermal magnetic entropy change ΔS{sub m}, has the maximum values of –19.8 J(kg K){sup −1} (at 4 K for 140 kOe field change) and −12.1 J(kg K){sup −1} (at 12 K for 140 kOe field change) in GdNi{sub 8}Si{sub 3} and TbNi{sub 8}Si{sub 3}, respectively. - Graphical abstract: GdNi{sub 8}Si{sub 3} and TbNi{sub 8}Si{sub 3} compounds are isostructural, and crystallize in a new monoclinic type strictly related to the tetragonal BaCd{sub 11} structure. The large R–R interatomic distances mediated via Ni–Si network lead to a weak magnetism in both compounds. - Highlights: • Novel RNi{sub 8}Si{sub 3} (R=Gd, Tb) compounds have been synthesized and characterized. • GdNi{sub 8}Si{sub 3} and TbNi{sub 8}Si{sub 3} are isostructural compounds, belonging to a new monoclinic structure type. • The monoclinic GdNi{sub 8}Si{sub 3} type is an ordered derivative of the tetragonal BaCd{sub 11} type. • The large R–R interatomic distances mediated via Ni–Si network lead to a weak magnetism. • Both compounds GdNi{sub 8}Si{sub 3} and TbNi{sub 8}Si{sub 3} show antiferromagnetic-like order around 3 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Novel phosphate halides BaMn{sup III}[PO{sub 4}]FCl and BaMn{sup III}[PO{sub 4}]F{sub 2}: Effects of mixed halides on crystal structures and magnetic properties

Two new phosphate halides BaMn{sup III}[PO{sub 4}]FCl (1) and BaMn{sup III}[PO{sub 4}]F{sub 2} (2), have been synthesized under hydrothermal conditions. Structural characterizations show that both new compounds adopt layered structures but with different polyhedral linkages. Introduction of Cl into Compound (1) results in isolated hemimorphic [MnO{sub 4}FCl] octahedra, different from the chain of [MnO{sub 4}F{sub 2}]/[MnO{sub 2}F{sub 4}] octahedra in Compound (2). These compounds have significantly different molecular vibration modes and thermal stabilities. Magnetic measurements reveal that Compound (2) has larger antiferromagnetic interactions than Compound (1), because the former has strong interactions between Mn{sup 3+}-Mn{sup 3+} ions within corner-shared Mn{sup 3+}-octahedral chains whereas the latter only possesses isolated Mn{sup 3+}-octahedra. Both compounds transform to a new orthorhombic compound BaMn{sup II}(PO{sub 4})F (3) after thermal decomposition. - Graphical abstract: The large radius of Cl{sup -} ions makesBaMn{sup III}[PO{sub 4}]FCl to adopt isolated [MnO{sub 4}FCl] rather than corner-sharing octahedra as observed in BaMn{sup III}[PO{sub 4}]F{sub 2}. - Highlights: • Two novel phosphate halides BaMn[PO{sub 4}]FCl and BaMn[PO{sub 4}]F{sub 2} have been prepared. • These new compounds adopt different types of layered structures. • They have different molecular vibration modes and thermal stabilities. • BaMn[PO{sub 4}]FCl has weaker antiferromagnetic interactions than BaMn[PO{sub 4}]F{sub 2}. • The former adopts isolated octahedra whereas the latter adopts octahedral chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗