Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “MONOCRYSTALS”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Growth and characterization of thin oriented Co{sub 3}O{sub 4} (111) films obtained by decomposition of layered cobaltates Na{sub x}CoO{sub 2}

The formation and structural characterization of highly (111)-oriented Co{sub 3}O{sub 4} films prepared by a novel procedure from weakly (001)-oriented Na{sub x}CoO{sub 2} is reported. The Na{sub x}CoO{sub 2} films were deposited on both single crystal and amorphous substrates by chemical solution deposition (CSD) method and crystallized at 700 °C. Subsequently they were transformed into (111)-oriented Co{sub 3}O{sub 4} phase during post-growth annealing at 900 °C. The degree of preferred orientation in Co{sub 3}O{sub 4}, which was determined by phi-scan and pole figure measurements, depends on the content of Na in the starting Na{sub x}CoO{sub 2} phase. Surface morphology of the films was investigated using electron microscopy and atomic force microscopy. - Graphical abstract: Structure of growth twins and possible O{sup 2−} stacking sequences in (111)-oriented Co{sub 3}O{sub 4} thin films on α-Al{sub 2}O{sub 3}(001) prepared by chemical solution deposition through the transformation of (001)-oriented Na{sub x}CoO{sub 2} thin film. - Highlights: • Single phase Co{sub 3}O{sub 4} thin films was prepared by means of chemical solution deposition. • Conditions for γ-Na{sub x}CoO{sub 2} to Co{sub 3}O{sub 4} transformation were optimized. • Growth twinning of Co{sub 3}O{sub 4} films due to two possible O{sup 2−} stacking sequences. • Growth with (pseudo)epitaxial relation Co{sub 3}O{sub 4} (111)[−121]//α-Al{sub 2}O{sub 3} (001)[10−10].

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis, structural characterization, luminescent properties and theoretical study of three novel lanthanide metal-organic frameworks of Ho(III), Gd(III) and Eu(III) with 2,5-thiophenedicarboxylate anion

In this paper, the synthesis of three new metal-organic frameworks of lanthanides (LnMOFs) ([Ln{sub 2}(2,5-tdc){sub 3}(dmso){sub 2}]·H{sub 2}O){sub n} (Ln=Ho (1); Gd (2); Eu (3); 2,5-tdc=2,5-thiophenedicarboxylate anion; dmso=dimethylsulfoxide), and their complete characterization, including single crystal X-ray diffraction, FTIR spectroscopy and thermogravimetric analysis are reported. In especial, photophysical properties of Eu(III) complex have been studied in detail via both theoretical and experimental approaches. Crystal structure of (1) reveals that each lanthanide ion is seven-coordinated by oxygen atoms in an overall distorted capped trigonal – prismatic geometry. The 2,5-tdc{sup 2−} ligands connect four Ln(III) centers, adopting (κ{sup 1}–κ{sup 1})–(κ{sup 1}–κ{sup 1})–μ{sub 4} coordination mode, generating an 8-connected uninodal 3D network. In addition, theoretical studies for Eu(III) complex were performed using the Sparkle model for lanthanide complexes. - Graphical abstract: Three new metal-organic frameworks of lanthanides (LnMOFs) ([Ln{sub 2}(2,5-tdc){sub 3}(dmso){sub 2}]·H{sub 2}O){sub n} (Ln=Ho (1); Gd (2); Eu (3); 2,5-tdc=2,5-thiophenedicarboxylate anion; dmso=dimethylsulfoxide), were synthesized and their complete characterization, including single crystal X-ray diffraction, FTIR spectroscopy and thermogravimetric analysis are reported. In especial, photophysical properties of Eu(III) complex have been studied in detail via both theoretical and experimental approaches. - Highlights: • Three new LnMOFs were synthesized and fully characterized. • Ho{sup 3+}, Gd{sup 3+} and Eu{sup 3+} complexes photoluminescence properties were investigated. • Theoretical approaches for Eu{sup 3+} complex luminescence has been performed. • An energy level diagram is used to establish the ligand-to-metal energy transfer. • These metal−organic frameworks can act as light conversion molecular devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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

The cluster compound In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} containing Mo{sub 14} clusters and the new mono- and bi-capped trioctahedral Mo{sub 15} and Mo{sub 16} clusters: Synthesis, crystal structure, and electrical and magnetic properties

Single crystals of the new quaternary compound In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} were obtained by solid state reaction. The crystal structure was determined by single-crystal X-ray diffraction. In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} crystallizes in the orthorhombic space group Pbca with unit-cell parameters a=9.4432(14) Å, b=11.4828(12) Å, c=20.299(4) Å and Z=4. Full-matrix least-squares refinement on F{sup 2} using 3807 independent reflections for 219 refinable parameters resulted in R{sub 1}=0.0259 and wR{sub 2}=0.0591. The crystal structure contains in addition to Mo{sub 14} clusters the first examples of mono- and bi-capped trioctahedral Mo{sub 14} i.e. Mo{sub 15} and Mo{sub 16} clusters. The oxygen framework derives from a stacking along the a direction of close-packed layers with sequence (…ABAC…). The Mo–Mo distances range between 2.6938(5) and 2.8420(6) Å and the Mo–O distances between 1.879(5) and 2.250(3) Å, as usually observed in molybdenum oxide clusters. The indium atoms form In{sub 4}{sup 6+} bent chains with In–In distances of 2.6682(5) and 2.6622(8) Å and the Ti atoms are in highly distorted octahedral sites of oxygen atoms with Ti–O distances ranging between 1.865(4) and 2.161(4) Å. Magnetic susceptibility measurements confirm the presence of Ti{sup 4+} cations and the absence of localized moments on the Mo network. Electrical resistivity measurements on a single crystal of In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} show a semimetallic behavior. - Graphical abstract: We present here the synthesis, the crystal structure, and the electrical and magnetic properties of the new compound In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} in which Mo{sub 14} clusters coexist statistically with mono- and bi-capped trioctahedral Mo{sub 14} that is Mo{sub 15} and Mo{sub 16} clusters. - Highlights: • Single crystals of In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} were obtained by solid state reaction. • The crystal structure contains Mo{sub 14}, Mo{sub 15} and Mo{sub 16} clusters. • The indium atoms form In{sub 4}{sup 6+} bent chains. • Poorly metallic behavior. • Absence of localized moments on the Mo network as well as on the Ti atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis, crystal structures, and physical properties of the new Zintl phases A{sub 21}Zn{sub 4}Pn{sub 18} (A=Ca, Eu; Pn=As, Sb)—Versatile arrangements of [ZnPn{sub 4}] tetrahedra

Four new Zintl phases, Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18} and Eu{sub 21}Zn{sub 4}Sb{sub 18} have been synthesized by metal flux reactions. Their structures have been established from single-crystal X-ray diffraction. Despite the similar chemical makeup and the identical formulae, the structures of the four compounds are not the same—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18} and Eu{sub 21}Zn{sub 4}As{sub 18} crystallize in the monoclinic space group C2/m (No. 12, Z=4) with the β-Ca{sub 21}Mn{sub 4}Sb{sub 18} structure type, while Eu{sub 21}Zn{sub 4}Sb{sub 18} adopts the Ba{sub 21}Cd{sub 4}Sb{sub 18} structure type with the orthorhombic space group Cmce (No. 64, Z=8). Both structures are based on ZnAs{sub 4} or ZnSb{sub 4} tetrahedra, linked in slightly different ways, and Ca{sup 2+} and Eu{sup 2+} cations that fill the space between them. The structural relationships between the title compounds and other known ternary phases with intricate structures are discussed. Electrical resistivity measurement on single-crystalline Eu{sub 21}Zn{sub 4}Sb{sub 18} suggests an intrinsic semiconductor behavior with a band gap of ca. 0.2 eV. The temperature dependent DC magnetization measurement on the same material indicates Curie–Weiss paramagnetism in the high-temperature regime, and a spontaneous antiferromagnetic ordering below 8 K. The calculated effective moments of Eu confirm the divalent Eu{sup 2+} ground state, as expected from the Zintl–Klemm concept. - Graphical abstract: The four new Zintl phases—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb{sub 18}—crystallize in two structure types, showing the versatility in the arrangements of ZnAs{sub 4} and ZnSb{sub 4} tetrahedra. - Highlights: • Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb{sub 18} are new compounds in the respective ternary phase diagrams. • They form with structure types, showing the versatility in the arrangements of ZnAs{sub 4} and ZnSb{sub 4} tetrahedra. • For both structures, the valence electron count follows the Zintl–Klemm rules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Crystal structure and thermal expansion of a CsCe{sub 2}Cl{sub 7} scintillator

We used single-crystal X-ray diffraction data to determine crystal structure of CsCe{sub 2}Cl{sub 7}. It crystallizes in a P112{sub 1}/b space group with a=19.352(1) Å, b=19.352(1) Å, c=14.838(1) Å, γ=119.87(2)°, and V=4818.6(5) Å{sup 3}. Differential scanning calorimetry measurements combined with the structural evolution of CsCe{sub 2}Cl{sub 7} via X-ray diffractometry over a temperature range from room temperature to the melting point indicates no obvious intermediate solid–solid phase transitions. The anisotropy in the average linear coefficient of thermal expansion of the a axis (21.3×10{sup –6}/°C) with respect to the b and c axes (27.0×10{sup –6}/°C) was determined through lattice parameter refinement of the temperature dependent diffraction patterns. These findings suggest that the reported cracking behavior during melt growth of CsCe{sub 2}Cl{sub 7} bulk crystals using conventional Bridgman and Czochralski techniques may be largely attributed to the anisotropy in thermal expansion. - Graphical abstract: Three-dimensional quadric surface of thermal expansion coefficient of CsCe{sub 2}Cl{sub 7} at room temperature (sphere – isotropic) and near melting point (ellipsoid – anisotropic). - Highlights: • Crystal structure of CsCe{sub 2}Cl{sub 7} was solved through X-ray diffraction. • Linear coefficients of thermal expansion were determined from in-situ XRD in 25–650 °C. • Anisotropy of the a axis with respect to b and c axes (21.3 vs 27.0×10{sup –6}/°C) was found. • No solid–solid phase transitions were observed via XRD and thermal analysis.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Ancillary ligand-assisted assembly of C{sub 3}-symmetric 4,4′,4″-nitrilotribenzoic acid with divalent Zn{sup 2+} ions: Syntheses, topological structures, and photoluminescence properties

4,4′,4″-nitrilotribenzoic acid (H{sub 3}L), a C{sub 3}-symmetric ligand, was found to self-assemble into two polymorphs driven by intermolecular hydrogen-bonding interactions. Reactions of this ligand with Zn{sup 2+} under solvothermal conditions resulted in four new coordination polymers bearing interesting structural motifs: [Zn{sub 2}(L){sub 2}(py){sub 2}]·2(H{sub 2}NMe{sub 2}){sup +}·DMF·2H{sub 2}O (1), [Zn{sub 2}(L)(H{sub 2}L)(bipy)]·1.5H{sub 2}O·Guest (2), [Zn{sub 2}(L){sub 2}(bipy)]·2(H{sub 2}NMe{sub 2}){sup +}·2DMF (3), and [Zn{sub 3}(L){sub 2}(bpa)]·2H{sub 2}O·Guest (4) (H{sub 3}L=4,4′,4′′-nitrilotribenzoic acid, DMF=dimethylformamide, py=pyridine, bipy=4,4′-bipyridine, bpa=1,2-bis(4-pyridyl)diazene). Single-crystal structural analysis revealed that compound 1 exhibits a rare example of twofold interpenetrating anionic 3D (3,3)-net framework containing helical channels, whereas in 2, the 3D pillar-layer structure generated from bipy-pillared Zn{sub 2}(L)(H{sub 2}L) layer is further reinforced by intermolecular hydrogen bonding among pairs of free –COOH units. Compound 3 shows an interesting entangled architecture of 2D→3D parallel polycatenation consisting five-coordinated Zn{sup 2+} ions. Compound 4 displays a 3D pillar-layer framework with trimeric Zn{sub 3}(CO{sub 2}){sub 6} serving as secondary building unit (SBU). The syntheses, structures, thermal stabilities, powder X-ray diffractions and solid-state photoluminescence properties for these crystalline materials have been carried out. In addition, supramolecular assembly of H{sub 3}L under solvothermal conditions will also be addressed. - Graphical abstract: Supramolecular assembly of 4,4′,4′′-nitrilotribenzoic acid and its ligand behavior toward Zn{sup 2+} were investigated, which exhibit two polymorphs of the free acid and four metal coordination polymers bearing interesting structural motifs. - Highlights: • Two polymorphs of H{sub 3}L showing different hydrogen-bonded network were obtained. • Tune over the structure of MOFs was achieved. • 1 has a 2-fold interpenetrating anionic 3D network containing helical channels. • Structures bearing free carboxylic acid (–COOH) unit are constructed in 2. • 3 represents a rare 2D+2D→3D catenation array containing five-coordinated Zn{sup 2+}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

New water soluble heterometallic complex showing unpredicted coordination modes of EDTA

A mesoporous 3D polymeric complex (I) having formula ([Zr(IV)O-μ{sup 3}-(EDTA)Fe(III)OH]·H{sub 2}O){sub n} has been crystallized and characterized by various techniques. Single-crystal X-ray diffraction analysis revealed that complex (I) crystallized in chiral monoclinic space group Cc (space group no. 9) with unexpected coordination modes of EDTA and mixture of two transition metal ions. In this complex, the coordination number of Zr(IV) ion is seven where four carboxylate oxygen atoms, two nitrogen atoms, one oxide atom are coordinating with Zr(IV). Fe(III) is four coordinated and its coordination environment is composed of three different carboxylic oxygen atoms from three different EDTA and one oxygen atom of –OH group. The structure consists of 4-c and 16-c (2-nodal) net with new topology and point symbol for net is (3{sup 36}·4{sup 54}·5{sup 30})·(3{sup 6}). TGA study and XRPD pattern showed that the coordination polymer is quite stable even after losing water molecule and –OH ion. Quenching behavior in fluorescence of ligand is observed by complexation with transition metal ions is due to n–π⁎ transition. The SEM micrograph shows the morphology of complex (I) exhibits spherical shape with size ranging from 50 to 280 nm. The minimum N{sub 2} (S{sub BET}=8.7693 m{sup 2}/g) and a maximum amount of H{sub 2} (high surface area=1044.86 m{sup 2}/g (STP)) could be adsorbed at 77 K. From DLS study, zeta potential is calculated i.e. −7.94 shows the negative charges on the surface of complex. Hirshfeld surface analysis and fingerprint plots revealed influence of weak or non bonding interactions in crystal packing of complex. - Graphical abstract: The complex (I) crystallized with unexpected coordination modes of EDTA having 4-c, 16-c net with new topology and point symbol is (3{sup 36}·4{sup 54}·5{sup 30})·(3{sup 6}). TGA study and XRPD pattern proved its stability with high preference of H{sub 2} uptake by complex. - Highlights: • 3D complex having unexpected coordination modes of EDTA with Zr(IV) and Fe(III). • The structure consists of 4-c and 16-c (2-nodal) net with new topology. • Reasonable S{sub BET} (8.7693 m{sup 2}/g) but high H{sub 2} uptake (1044.86 m{sup 2}/g) due to limited pore size. • Quenching behavior due to n–π⁎ transition by complexation with transition metal ions. • From DLS study, zeta potential value is −7.94.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Phase equilibria in the quasiternary system Ag{sub 2}S–Ga{sub 2}S{sub 3}–In{sub 2}S{sub 3} and optical properties of (Ga{sub 55}In{sub 45}){sub 2}S{sub 300}, (Ga{sub 54.59}In{sub 44.66}Er{sub 0.75}){sub 2}S{sub 300} single crystals

The quasiternary system Ag{sub 2}S–Ga{sub 2}S{sub 3}–In{sub 2}S{sub 3} was investigated by differential thermal, X-ray diffraction analyses. The phase diagram of the Ga{sub 2}S{sub 3}–In{sub 2}S{sub 3} system and nine polythermal sections, isothermal section at 820 K and the liquidus surface projection were constructed. The existence of the large solid solutions ranges of binary and ternary compounds was established. The range of the existence of the quaternary phase AgGa{sub x}In{sub 5−x}S{sub 8} (2.25≤x≤2.85) at 820 K was determined. The single crystals (Ga{sub 55}In{sub 45}){sub 2}S{sub 300} and (Ga{sub 54.59}In{sub 44.66}Er{sub 0.75}){sub 2}S{sub 300} were grown by a directional crystallization method from solution-melt. Optical absorption spectra in the 500–1600 nm range were recorded. The luminescence of the (Ga{sub 54.59}In{sub 44.66}Er{sub 0.75}){sub 2}S{sub 300} single crystal shows a maximum at 1530 nm for the excitation wavelengths of 532 and 980 nm at 80 and 300 K. - Graphical abstract: Isothermal section of the quasiternary system Ag{sub 2}S–Ga{sub 2}S{sub 3}–In{sub 2}S{sub 3} at 820 K and normalized photoluminescence spectra of the single crystal (Ga{sub 54.59}In{sub 44.66}Er{sub 0.75}){sub 2}S{sub 300} at 300 K. - Highlights: • Isothermal section at 820 K, liquidus surface projection were built for Ag{sub 2}S–Ga{sub 2}S{sub 3}–In{sub 2}S{sub 3}. • Optical properties of single crystals were studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Temperature-dependent ordering phenomena in single crystals of germanium antimony tellurides

The temperature-dependent behavior of quenched single-crystalline (GeTe){sub n}Sb{sub 2}Te{sub 3} (n~2.8, n~5 and n~11) was investigated by semiquantitative modeling of diffuse X-ray scattering. The structure at room temperature exhibits trigonal twin domains, each comprising a stacking-disordered sequence of distorted rocksalt-type slabs with variable thicknesses. Ge and Sb share the cation position and vacancies are partially ordered in defect layers (van der Waals gaps) between the slabs. The average structure determined with resonant diffraction data corresponds to a rocksalt-type structure whose cation position is split along the stacking direction. Upon heating, cation ordering leads to a metastable superstructure of the rocksalt type at ~400 °C, which transforms to a rocksalt-type high-temperature phase with randomly distributed cations and vacancies at ~500 °C; this structure was also refined using resonant diffraction. Cooling at high or intermediate rates does not yield the long-range ordered phase, but directly leads to the twinned disordered phase. - Graphical abstract: Development of the diffraction patterns of (GeTe){sub ~11}Sb{sub 2}Te{sub 3} upon heating; the insets symbolically sketch the real structure at the corresponding temperatures. - Highlights: • The structure of disordered (GeTe){sub n}Sb{sub 2}Te{sub 3} is described as a function of temperature. • Structural changes are tracked by modeling diffuse X-ray scattering. • Quenched crystals exhibit distorted NaCl-type slabs with different thicknesses. • Vacancy ordering upon heating leads to a metastable superstructure of the NaCl type. • Further heating leads to an undistorted disordered NaCl-type high-temperature phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Three luminescent d{sup 10} metal coordination polymers assembled from a semirigid V-shaped ligand with high selective detecting of Cu{sup 2+} ion and nitrobenzene

Three 2D luminescent coordination polymers with helical frameworks, [ZnL{sub 2}]{sub n} (1) and ([ML{sub 2}]·(H{sub 2}O)){sub n} (M=Zn (2), Cd (3)) (HL=4-((2-methyl-1 H-imidazol-1-yl)methyl)benzoic acid), have been assembled under hydro(solvo)thermal conditions. Complex 1 is in chiral space group and displays a rare 2D→2D 2-fold parallel interpenetrated layer network with two types of chiral double helixes. Interestingly, the single crystal structure analyses indicate the coexistence of enantiomers la and 1b in one pot, while the bulk crystallization of 1 are racemic mixtures based on the CD measurement. 2 and 3 are isostructural, in the structure, there are two kinds of 2D chiral helical-layers which stack in an -ABAB- sequence leading to the overall structure are mesomer and achiral. All compounds display intense luminescence in solid state at room temperature with high chemical and thermal stability. More importantly, 1 has been successfully applied in the detection of Cu{sup 2+} ions in aqueous media and nitrobenzene and the probable detecting mechanism was also discussed. - Graphical abstract: Three luminescent d{sup 10} metal coordination polymers with helical-layer based on 4-((2-methyl-1H-imidazol-1-yl)methyl)benzoic acid have been obtained. Compound 1 shows high selective detecting for Cu{sup 2+} ion in aqueous and nitrobenzene. - Highlights: • Three coordination polymers with chiral helical-layer have been obtained. • 1 Can luminescent detect Cu{sup 2+} ion in aqueous media and nitrobenzene. • Racemic mixture or mesomer compounds can be obtained by controlling the reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A nanoporous 3D zinc(II) metal–organic framework for selective absorption of benzaldehyde and formaldehyde

A new 3D nanoporous metal–organic framework (MOF), [[Zn{sub 4}O(C{sub 24}H{sub 15}N{sub 6}O{sub 6}){sub 2}(H{sub 2}O){sub 2}]·6H{sub 2}O·DMF]{sub n} (1) based on 4,4′,4″-s-triazine-1,3,5-triyltri-p-aminobenzoate (TATAB) ligand was solvothermally synthesized and characterized by single–crystal X-ray diffraction, Powder X-ray diffraction (PXRD), infrared spectroscopy (IR) and Brunauer–Emmett–Teller (BET) analyses. X-ray single crystal diffraction analysis reveals that 1 exhibits a 3D network with new kvh1 topology. Semi-empirical (AM1) calculations were carried out to obtain stable conformers for TATAB ligand. In addition, the absorption of two typical aldehydes (benzaldehyde and formaldehyde) in the presence of 1 was investigated and the effect of the aldehyde concentration, exposure time and temperature was studied. It was found that compound 1 has a potential for the absorption of aldehydes under mild conditions. - Graphical abstract: Absorption of two typical aldehydes (formaldehyde and benzaldehyde) by solvothermally synthesized of a 3D nano-porous MOF based on TATAB tricarboxylate ligand and Zn (NO{sub 3}){sub 2}·6H{sub 2}O. - Highlights: • We present a 3D Zn(II)-MOF with TATAB linker by solvothermal method. • The framework possesses a new kvh1 topology. • The framework displays formaldehyde and benzaldehyde absorption property. • Conformational analysis was performed to determine the stable linker geometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

High-pressure synthesis and crystal structures of the strontium oxogallates Sr{sub 2}Ga{sub 2}O{sub 5} and Sr{sub 5}Ga{sub 6}O{sub 14}

High-pressure synthesis experiments in a piston–cylinder apparatus at 1.5 GPa/3.0 GPa and 1000 °C resulted in the formation of single-crystals of Sr{sub 2}Ga{sub 2}O{sub 5} and Sr{sub 5}Ga{sub 6}O{sub 14}, respectively. The structures of both compounds have been solved from single-crystal diffraction data sets using direct methods. The first compound is orthorhombic with space group type Pbca (a=10.0021(4) Å, b=9.601(4) Å, c=10.6700(4) Å, V=1024.6(4) Å{sup 3}, M{sub r}=394.68 u, Z=8, D{sub x}=5.12 g/cm{sup 3}) and belongs to the group of single layer gallates. Individual sheets are parallel to (0 0 1) and can be built from the condensation of unbranched vierer single chains running along [0 1 0]. The layers are characterized by the presence of four- and strongly elliptical eight-membered rings of corner connected tetrahedra in UUDD and UUUUDDDD conformation. Strontium atoms are sandwiched between the tetrahedral layers for charge compensation and are coordinated by six and seven oxygen ligands, respectively. Sr{sub 2}Ga{sub 2}O{sub 5} is isotypic with several other double sulfides and selenides. To the best of our knowledge, it is the first example of an oxide with this structure type. From a structural point of view, Sr{sub 5}Ga{sub 6}O{sub 14} is a phyllogallate as well. The crystal structure adopts the monoclinic space group P2{sub 1}/c (a=8.1426(3) Å, b=8.1803(3) Å, c=10.8755(4) Å, β=91.970(4)° V=723.98(5) Å{sup 3}, M{sub r}=1080.42 u, Z=2, D{sub x}=4.96 g/cm{sup 3}). Individual sheets extend along (0 0 1). Basic building units are unbranched dreier single chains parallel to [1 0 0]. The layers contain tertiary (Q{sup 3}) und quaternary (Q{sup 4}) connected [GaO{sub 4}]-tetrahedra in the ratio 2:1 resulting in a Ga:O ratio of 3:7 and the formation of exclusively five-membered rings. Linkage between adjacent tetrahedral sheets is provided by three symmetrically independent strontium ions which are surrounded by six to eight oxygen atoms. The layers in Sr{sub 5}Ga{sub 6}O{sub 14} are similar to those observed in the melilite structure-type. Crystallochemical relationships between the present phases and other known compounds are discussed in detail. - Graphical abstract: A single tetrahedral layer and the location of the Sr-cations directly above the sheet in high-pressure Sr{sub 5}Ga{sub 6}O{sub 14}. - Highlights: • We report the crystal structures of two new strontium oxogallates with composition Sr{sub 2}Ga{sub 2}O{sub 5} and Sr{sub 5}Ga{sub 6}O{sub 14.} • Both phases have been obtained in the course of high-pressure piston–cylinder experiments performed at 1.5 and 3.0 GPa. • The crystallochemical characteristics and similarities with known structure types are discussed in detail.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Syntheses, characterization and properties of silver, copper and palladium complexes from bis(oxazoline)-containing ligands

The reactions of 2,6-di(2-oxazolyl)pyridine (L{sup 1}) and 2,6-bis[(S)-4-phenyl-2-oxazolyl]pyridine (L{sup 2}) with silver, copper and palladium salts to yield six new complexes: ([Ag{sub 5}(L{sup 1}){sub 5}](BF{sub 4}){sub 5}){sub n} (1), ([Ag(L{sup 1})](SbF{sub 6})){sub n} (2), [Cu{sub 4}I{sub 4}(L{sup 1}){sub 2}] (3), [Cu{sub 6}I{sub 6}(L{sup 1}){sub 2}] (4), [Pd(L′{sup 1})(OAc)] (5), [Pd(L′{sup 2})Cl] (6), which were fully characterized by single-crystal and powder X-ray diffraction, IR, elemental and thermogravimetric analyses. 1 and 2 are a pair of Ag-oxazoline helical chain structure complexes. The spiral directions of chains are opposite in 1, while identical in 2; the measurement of CD spectra can further confirm their meso and chiral structures. Complexes 3 and 4 show eight-nuclear and twelve-nuclear iodine–cuprous cluster structure. Their structural diversity is induced by different molar ratios of CuI:L{sup 1}. Complexes 5 and 6 are discrete mononuclear palladium complexes. In situ oxazolyl-ring-opening reactions take place in the syntheses of them and the L{sup 1} and the L{sup 2} were transformed to their oxazolyl-ring opened derivatives L′{sup 1} and L′{sup 2}. Moreover, fluorescence, non-linear optical properties, and ferroelectric properties have been investigated. - Graphical abstract: 2,6-di(2-oxazolyl)pyridine (L{sup 1}) reacts with silver and copper salts to yield helical and cluster structure complexes. - Highlights: • Helical and cluster structure complexes. • In situ oxazolyl-ring-opening reactions. • Fluorescence, non-linear optical properties, and ferroelectric properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Utilization of mixed ligands to construct two new coordination polymers: Syntheses, structures and properties

The use of triazine and aromatic carboxylic acid as mixed chelating ligands in preparing two coordination polymers is described. Two new transition-metal coordination polymers, namely, [Co{sub 2}(bpdc){sub 4}(phdat){sub 2}] (1) and [Zn(bpdc)]{sub n} (2) (H{sub 2}bpdc=2,4-biphenyldicarboxylic acid, phdat=2,4-diamine-6-phenyl-1,3,5-triazine), have been hydrothermally synthesized and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. Compound 1 is a 0D structure and extends to a 3D network by two different N–H···O and N–H···N hydrogen bonds. Compound 2 exhibits a 2D network with 4{sup 4}.6{sup 2} topological net, which contains two kinds of single helical chains. The interactions within each Co(II)–Co(II) pair of compound 1 are antiferromagnetic (g=2.19, J=−22 K, zj′=−0.00351 K). Furthermore, the photoluminescence property of 2 was also investigated in the solid state at room temperature. - Graphical abstract: Two polymeric metal compounds based on mixed-ligands were synthesized and characterized. The use of different metal ions results in distinct structures. The magnetic and fluorescent properties were also studied. - Highlights: • The first bpdc{sup 2−}/phdat-based 0D discrete coordination complex. • A new 2D architecture with two kinds of helical chains. • The structure-dependent magnetism and photoluminescence properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Mild hydrothermal crystal growth of new uranium(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30}: Structures, optical and magnetic properties

Two new uranium(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} (1) and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30} (2), were synthesized through an in situ mild hydrothermal route, and were structurally characterized by single crystal X-ray diffraction. The compounds exhibit complex crystal structures composed of corner- or edge-shared UF{sub 9} and MF{sub 6} (M=Mg, Mn) polyhedra, forming hexagonal channels in the three-dimensional framework, in which ordered or disordered divalent metal and sodium atoms reside. The large hexagonal voids contain the nearly regular M(II)F{sub 6} octahedra and sodium ions, whereas the small hexagonal cavities include M(II) and sodium ions on a mixed-occupied site. Magnetic susceptibility measurements yielded effective magnetic moments of 8.36 and 11.6 µ{sub B} for 1 and 2, respectively, confirming the presence and oxidation states of U(IV) and Mn(II). The large negative Weiss constants indicate the spin gap between a triplet and a singlet state in the U(IV). Magnetization data as a function of applied fields revealed that 2 exhibits paramagnetic behavior due to the nonmagnetic singlet ground state of U(IV) at low temperature. UV–vis diffuse reflectance and X-ray photoelectron spectroscopy data were also analyzed. - Graphical abstract: Two new quaternary U(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30}, were crystallized via an in situ reduction step of U(VI) to U(IV) under mild hydrothermal conditions. The compounds show complex crystal structures based on the 3-D building block of U{sub 6}F{sub 30}. Magnetic property measurements revealed that the U(IV) exhibits a nonmagnetic singlet ground state at low temperature with a spin gap. - Highlights: • Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30} have been synthesized and characterized. • The U(IV) fluorides exhibit complex three-dimensional crystal structures. • The optical properties were investigated. • Magnetic susceptibility data were collected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Topologically and geometrically flexible structural units in seven new organically templated uranyl selenates and selenite–selenates

Single crystals of seven novel uranyl oxysalts of selenium with protonated methylamine molecules, [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (I), [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O)] (II), [C{sub 4}H{sub 15}N{sub 3}][H{sub 3}O]{sub 0.5}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 2.93}(SeO{sub 3}){sub 0.07}(H{sub 2}O)](NO{sub 3}){sub 0.5} (III), [C{sub 2}H{sub 8}N]{sub 3}[H{sub 5}O{sub 2}][(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub 2}(H{sub 2}O){sub 5} (IV), [C{sub 2}H{sub 8}N]{sub 2}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 4}(HSeO{sub 3})(H{sub 2}O)](H{sub 2}SeO{sub 3}){sub 0.2} (V), [C{sub 4}H{sub 12}N]{sub 3}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 5}(H{sub 2}O)] (VI), and [C{sub 2}H{sub 8}N]{sub 3}(C{sub 2}H{sub 7}N)[(UO{sub 2}){sub 3}(SeO{sub 4}){sub 4}(HSeO{sub 3})(H{sub 2}O)] (VII) have been prepared by isothermal evaporation from aqueous solutions. Their crystal structures have been solved by direct methods and their uranyl selenate and selenite–selenate units investigated using black-and-white graphs from the viewpoints of topology of interpolyhedral linkages and isomeric variations. The crystal structure of IV is based upon complex layers with unique topology, which has not been observed previously in uranyl selenates. Investigations of the statistics and local distribution of the U–O{sub br}–Se bond angles demonstrates that shorter angles associate with undulations, whereas larger angles correspond to planar areas of the uranyl selenite layers. - Graphical abstract: Crystal structures of the seven novel Se-contaning uranyl oxysalts that contain protonated organic molecules as interlayer species have been investigated from the viewpoints of topology of interpolyhedral linkages, isomeric variations and flexibility of structural units. - Highlights: • Single crystals of seven novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • The method of orientation matrices was applied to distinguish geometrical isomers. • The flexibility of structural complexes specifies the undulation of layered structural units.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Syntheses, crystal structures, and properties of four complexes based on polycarboxylate and imidazole ligands

Four metal–organic coordination polymers [Zn(HL)(H{sub 2}O)]·4H{sub 2}O (1), [Zn(HL)(L{sub 1})]·4H{sub 2}O (2), [Cu(HL)(H{sub 2}O)]·3H{sub 2}O (3) and [Cu(HL)(L{sub 1})]·5H{sub 2}O (4) were synthesized by reactions of the corresponding metal(II) salts with semirigid polycarboxylate ligand (5-((4-carboxypiperidin-1-yl)methyl)isophthalic acid hydrochloride, H{sub 3}L·HCl) or auxiliary ligand (1,4-di(1H-imidazol-4-yl)benzene, L{sub 1}). The structures of the compounds were characterized by elemental analysis, FT-IR spectroscopy and single-crystal X-ray diffraction. The use of auxiliary ligand L{sub 1} has great influence on the structures of two pairs of complexes 1, 2 and 3, 4. Complex 1 is a uninodal 3-connected rare 2-fold interpenetrating ZnSc net with a Point (Schlafli) symbol of (10{sup 3}) while 2 is a one-dimensional (1D) ladder structure. Compound 3 features a two-dimensional (2D) honeycomb network with typical 6{sup 3}-hcb topology, while 4 is 2D network with (4, 4) sql topology based on binuclear Cu{sup II} subunits. The non-covalent bonding interactions such as hydrogen bonds, π···π stacking and C–H···π exist in complexes 1–4, which contributes to stabilize crystal structure and extend the low-dimensional entities into high-dimensional frameworks. And the photoluminescent property of 1 and 2 and gas sorption property of 4 have been investigated. - Graphical abstract: Four new coordination polymers have been obtained and their photoluminescent and gas sorption properties have also been investigated. - Highlights: • Two pairs of Zn{sup II}/ Cu{sup II} compounds have been synthesized. • Auxiliary ligand-controlled assembly of the complexes is reported. • The luminescent properties of complexes 1–2 were investigated. • The gas sorption property of 4 has been investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗