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At least 577 records · Page 32
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DOE OSTI2013

Ternary aluminides R{sub 0.67}Ni{sub 2}Al{sub 6} (R=Sc, Y, Gd-Lu) with partly disordered structures

Ten rare-earth nickel aluminides R{sub 0.67}Ni{sub 2}Al{sub 6} (R=Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were synthesized by arc melting and their crystal structures studied by X-ray powder diffraction. They crystallize in the hexagonal structure type Yb{sub 0.67}Ni{sub 2}Al{sub 6}: Pearson symbol hP11-2.33, space group P-6m2, a=4.18904(2), c=9.09816(6) A, which can be decomposed into three kinds of layer. The sequence of layers along [001] is Yb{sub 0.67}Al-NiAl{sub 2}-Al-NiAl{sub 2}, but stacking faults appear due to relative shifts of consecutive Yb{sub 0.67}Al layers containing two rare-earth metal atoms for one Al-atom triangle. An ordered superstructure is the type ErNi{sub 3}Al{sub 9} (Pearson symbol hR78, space group R32, a={radical}(3)a{sub 0}, c=3c{sub 0}), refined on single crystals. The physical properties of the R{sub 0.67}Ni{sub 2}Al{sub 6} (R=Tb, Er, Tm, Yb, and Lu) compounds were determined by means of magnetic and electrical transport measurements. All these materials but Lu{sub 0.67}Ni{sub 2}Al{sub 6} exhibit Curie-Weiss paramagnetic behavior due to the trivalent R ions, and order magnetically at low temperatures. They show good metallic conductivity. The Yb-containing compound is a dense Kondo system with distinct features in the paramagnetic state of the interplay between Kondo and crystalline electric field interactions. - Graphical abstract: Stacking of layers along [001] in the Yb{sub 0.67}Ni{sub 2}Al{sub 6}-type structure. Highlights: Black-Right-Pointing-Pointer The aluminides R{sub 0.67}Ni{sub 2}Al{sub 6} (R=Sc, Y, Gd-Lu) adopt a partly disordered structure. Black-Right-Pointing-Pointer The structure is characterized by R{sub 2}Al{sub 3} layers with two R atoms for one Al{sub 3} triangle. Black-Right-Pointing-Pointer The compounds with R=Tb, Er, Tm are paramagnets at rt and order magnetically at lt. Black-Right-Pointing-Pointer The Yb-compound exhibits a magnetically ordered Kondo lattice with strong CEF effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Three new Ag(I) coordination architectures based on mixed ligands: Syntheses, structures and photoluminescent properties

Three new silver (I) coordination complexes, [Ag{sub 2}(1,2-bdc)(phdat)]{sub n} (1), [Ag{sub 2}(NO{sub 2}-bdc)(phdat)]{sub n} (2), [Ag{sub 4}(nta){sub 3}(phdat)NO{sub 3}]{sub n} (3) (1,2-bdc=phthalic acid dianion, NO{sub 2}-bdc=5-nitro-1,3-benzenedicarboxylic acid dianion, nta=nicotinic acid anion, phdat=2,4-diamine-6-phenyl-1,3,5-triazine) have been hydrothermally synthesized by the reactions of silver nitrate and phdat with the homologous ligands 1,2-H{sub 2}bdc, NO{sub 2}-H{sub 2}bdc, and Hnta, respectively, and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses thermogravimetric analyses (TGA). The compound 1 exhibits a chiral 3D network with cbs/CrB self-dual topological net, which contains two kinds of single helical chains. For compound 2, the 3D network is comprised of two kinds of similar 2D sheets with the topological symbol of sql-type packed in AABBAA mode by Ag–N/O weakly contacts. And compound 3 has 2D double layer architecture, consisting of the 2D plane with hcb-type topological symbol connected by Ag–O weakly coordinations. The photoluminescent properties associated with the crystal structures of three compounds have also been measured. - Graphical abstract: Three new silver(I) coordination complexes 1–3 have been synthesized and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses, thermogravimetric analyses (TGA) and photoluminescent spectra. Highlights: ► The compound 1 exhibits a novel chiral 3D network with two kinds of single helical chains. ► 3D or 2D new Ag coordination complexes. ► The photoluminescent properties have been measured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

The Y{sub 5−x}Mg{sub 24+x}(1.08(4)≤x≤1.30(1)) series and a ternary derivative Ce{sub 6.9}Y{sub 12.5(7)}Mg{sub 92.2}: A comparison of their crystal and electronic structures

The Y{sub 5−x}Mg{sub 24+x} series and a ternary derivative, Ce{sub 0.36}Y{sub 0.64(2)}Mg{sub 4.76}, have been synthesized using high-temperature methods and characterized by both powder and single crystal X-ray diffraction. The Y{sub 5−x}Mg{sub 24+x} series upon quenching from 580 °C crystallizes over the range 1.08(4)≤x≤1.30(1) in the cubic α-Mn structure type (I4{sup ¯}3m, Z=2, Pearson symbol cI58) with mixed occupancy of Y and Mg at the 8c site. As Mg content increases, the corresponding lattice parameter a increases from 11.2337(6) Å for Y{sub 3.92(4)}Mg{sub 25.08} to 11.256(2) Å for Y{sub 3.70(1)}Mg{sub 25.30}. Attempts to replace Y atoms with larger, isovalent Ce atoms yielded Ce{sub 6.9}Y{sub 12.5(7)}Mg{sub 92.2}(=Ce{sub 0.36}Y{sub 0.64(2)}Mg{sub 4.76}), which adopts a defect Sm{sub 11}Cd{sub 45} structure type (F4{sup ¯}3m, Z=8, Pearson symbol cF446.4), with a lattice parameter a=22.443(2) Å that is nearly twice larger than those of the Y{sub 5−x}Mg{sub 24+x} series. The complex crystal structure of this ternary derivative can be described as an ordered, body-centered cubic packing of four chemically and structurally distinctive “nested-polyhedra,” two 27-atom and two 29-atom, α-Mn units. Electronic structure calculations show nearly free electron like behavior, but with a distinctive pseudogap in the density of states curve for the ternary system. - Graphical abstract: Reported is the Mg-rich intermetallic compounds Y{sub 5−x}Mg{sub 24+x} series adopting the cubic α-Mn type structure and its complex ternary derivative Ce{sub 6.9}Y{sub 12.5}Mg{sub 92.2} crystallized in a defect Sm{sub 11}Cd{sub 45} type structure with a nearly twice larger lattice parameter than those of the Y{sub 5−x}Mg{sub 24+x} series. Electronic structure calculations show nearly free electron like behavior, but with a distinctive pseudogap in the density of states curve for the ternary system. Highlights: • The Y{sub 5−x}Mg{sub 24+x} series and Ce{sub 6.9}Y{sub 12.5}Mg{sub 92.2} have been synthesized. • Ce{sub 6.9}Y{sub 12.5}Mg{sub 92.2} is seen as a body-centered cubic packing of “nested-polyhedra”. • Electronic structures show nearly free electron like behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Synthesis, characterization, magnetic and electrochemical properties of a new 3D hexa-copper-substituted germanotungstate

An inorganic–organic hybrid hexa-copper-substituted germanotungstate Na{sub 2}[Cu(dap){sub 2}]{sub 2}[Cu(dap){sub 2}] ([Cu{sub 6}(H{sub 2}O){sub 2}(dap){sub 2}][B-α-GeW{sub 9}O{sub 34}]{sub 2})·4H{sub 2}O (1) (dap=1,2-diaminopropane) has been hydrothermally prepared and characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP–AES) analyses, IR spectra, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. 1 displays the six-connected 3D network with the long topological (O′Keefe) vertex symbol is 4·4·6{sub 4}·4·4·4·4·6{sub 4}·4·4·4·6{sub 4}·4·4·4 and the short vertex (Schläfli) symbol of 4{sup 12}6{sup 3}. Magnetic measurements indicate that there are the overall ferromagnetic exchange interactions in the belt-like hexa-Cu{sup II} cluster in 1. Furthermore, the electrochemical behavior and electrocatalysis of 1 modified carbon paste electrode (1-CPE) have been studied. The reductions of nitrite, bromate and hydrogen peroxide are principally mediated by the W{sup VI}-based wave. - Graphical abstract: A hexa-Cu{sup II} sandwiched germanotungstate has been synthesized and structurally characterized. The magnetic, solid-state electrochemical and electrocatalytic properties have been investigated. Display Omitted - Highlights: • Transition-metal substituted polyoxometalates. • Hexa-copper-substituted germanotungstate. • Six-connected 3D network. • Electrocatalytic reduction of nitrite, bromate and hydrogen peroxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

The layered antimonides RELi{sub 3}Sb{sub 2} (RE=Ce–Nd, Sm, Gd–Ho). Filled derivatives of the CaAl{sub 2}Si{sub 2} structure type

Reported are the synthesis and the structural characterization of an extended family of rare-earth metal–lithium–antimonides with the formula RELi{sub 3}Sb{sub 2} (RE=Ce–Nd, Sm, Gd–Ho). They crystallize in the trigonal space group P3{sup ¯}m1 (No. 164, Pearson symbol hP6) with a structure, best viewed as a filled derivative of the common CaAl{sub 2}Si{sub 2} structure type (ternary variant of α-La{sub 2}O{sub 3}). Across the series, the lattice parameters monotonically decrease, following the lanthanide contraction. Temperature-dependent magnetic susceptibility measurements for CeLi{sub 3}Sb{sub 2}, PrLi{sub 3}Sb{sub 2} and TbLi{sub 3}Sb{sub 2} reveal paramagnetic behavior in the high temperature range, and the obtained effective moments are consistent with the expected ones for the free-ion RE{sup 3+} ground state. Possible ferromagnetic ordering for PrLi{sub 3}Sb{sub 2} and antiferromagnetic ordering for TbLi{sub 3}Sb{sub 2} are observed in the low temperature range (below 20 K). Tight-binding muffin-tin orbital electronic band structure calculations for LaLi{sub 3}Sb{sub 2} are presented and discussed as well. - Graphical abstract: The large family of rare-earth metal–lithium–antimonides with the formula RELi{sub 3}Sb{sub 2} (RE=Ce–Nd, Sm, Gd–Ho) crystallize in the trigonal space group P3{sup ¯}m1 (No. 164, Pearson symbol hP6) with a structure that is a filled derivative of the CaAl{sub 2}Si{sub 2} structure type (ternary variant of α-La{sub 2}O{sub 3}). Display Omitted - Highlights: • RELi{sub 3}Sb{sub 2} (RE=Ce–Nd, Sm, Gd–Ho) constitute an extended family of rare-earth metal–lithium–antimonides. • The layered structure is a filled derivative of the common CaAl{sub 2}Si{sub 2} structure type. • The valence electron count follows the Zintl–Klemm rules. • Electronic band structure calculations for LaLi{sub 3}Sb{sub 2} indicate small band-gap semiconducting behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Gas adsorption/separation properties of metal directed self-assembly of two coordination polymers with 5-nitroisophthalate

Two new coordination polymers, namely, [Co(µ-nip)(µ-bpe)]{sub n} (1) and [Zn(µ-nip)(µ-bpe)]{sub n} (2) (nip: 5-nitroisophthalate, bpe: 1,2-bis(4-pyridyl)ethane) were hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermal analysis. Moreover, atomically detailed simulation studies of complex 2 for CO{sub 2}/CH{sub 4} adsorption and separation were performed. Complex 1 consists of two dimensional (2D) (4,4) grid networks with the point symbol of 4{sup 4}.6{sup 2}. Complex 2 exhibits a 3-fold interpenetrating 3D framework with 6{sup 5}.8-dmp topology. Thermal properties of the complexes showed that both complexes were stable over 320 °C. Simulation studies demonstrated that complex 2 can separate CO{sub 2} from CH{sub 4} at low pressures at 273 K. - Graphical abstract: In this study, two new coordination polymers, namely, [Co(µ-nip)(µ-bpe)]{sub n} (1) and [Zn(µ-nip)(µ-bpe)]{sub n} (2) (nip: 5-nitroisophthalate, bpe: 1,2-bis(4-pyridyl)ethane) were hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermal analysis. Moreover, atomically detailed simulation studies of complex 2 for CO{sub 2}/CH{sub 4} adsorption and separation were performed. Complex 1 consists of two dimensional (2D) (4,4) grid networks with the point symbol of 4{sup 4}.6{sup 2}. Complex 2 exhibits a 3-fold interpenetrating 3D framework with 6{sup 5}.8-dmp topology. Simulation studies demonstrated that complex 2 can separate CO{sub 2} from CH{sub 4} at low pressures at 273 K. Display Omitted - Highlights: • Two new coordination polymers with 5-nitroisophthalate and 1,2-bis(4-pyridyl)ethane. • Atomically detailed simulation studies of the complexes. • Complex 2 can be proposed as molecular sieve to separate CO{sub 2} from CH{sub 4} at low pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Two new pyridine-2,3-dicarboxylate coordination polymers prepared from zerovalent metal precursor: Syntheses, luminescent and magnetic properties

Two new K{sup +}/Cu(II) and Zn(II) coordination polymers with pyridine-2,3-dicarboxylate (pydc), (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} (1) and ([Zn(µ-pydc)(H{sub 2}O)(4-mim)]·H{sub 2}O){sub n} (2) (4-mim=4-methylimidazole) have been synthesized from zerovalent metal and characterized by IR, EPR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. In the sandwiched 3D anionic framework of 1, pydc ligands exhibit hexadentate coordination; tridentate coordination bond with Cu(II) and tridentate ionic interaction with K{sup +} ions. (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} shows a rare topology consists of three dimensional (3,4,5)-connected network with the point symbol of (4{sup 2}.6){sub 2}(4{sup 2}.8{sup 4})(4{sup 3}.6.8{sup 6}){sub 2}. The distorted square pyramidal geometry of 2 is completed with an nitrogen atom from 4-mim and aqua ligand to form a 1D polynuclear structure. The hydrogen bonds link the 1D chains into 3D architecture. The temperature dependent magnetic property of complex 1 has been studied. Complex 2 exhibits unusual yellow luminescence in the solid state at room temperature. - Graphical abstract: Two new K{sup +}/Cu(II) and Zn(II) coordination polymers with pyridine-2,3-dicarboxylate (pydc), (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} (1) and ([Zn(µ-pydc)(H{sub 2}O)(4-mim)]·H{sub 2}O){sub n} (2) (4-mim=4-methylimidazole) have been synthesized from zerovalent metal and characterized by IR, EPR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. The water soluble (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} shows three dimensional a rare 3,4,5-connected network with the point symbol of (4{sup 2}.6){sub 2}(4{sup 2}.8{sup 4})(4{sup 3}.6.8{sup 6}){sub 2}. The temperature dependent magnetic property of complex 1 has been studied. Complex 2 exhibits unusual yellow luminescence in the solid state at room temperature. Display Omitted - Highlights: • Water-soluble (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} has synthesized. • Zerovalent metal precursors are utilized. • The temperature dependent magnetic properties have been studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

2D→3D polycatenated and 3D→3D interpenetrated metal–organic frameworks constructed from thiophene-2,5-dicarboxylate and rigid bis(imidazole) ligands

Hydrothermal reactions of rigid 1,4-bis(imidazol-1-yl)benzene (dib) and 1,4-bis(imidazol-1-yl)-2,5-dimethylbenzene (dimb) with deprotonated thiophene-2,5-dicarboxylic acid (H{sub 2}tdc) in the presence of Zn(II) and Cd(II) salts in H{sub 2}O produced three new metal–organic frameworks, namely, [Zn(µ-tdc)(H{sub 2}O)(µ-dib)]{sub n} (1), [Cd(µ-tdc)(H{sub 2}O)(µ-dib)]{sub n} (2), and ([Cd{sub 2}(µ{sub 3}-tdc){sub 2}(µ-dimb){sub 2}]·(H{sub 2}O)){sub n}(3). These MOFs were characterized by FT-IR spectroscopy, elemental, thermal (TG, DTA, DTG and DSC), and single-crystal X-ray diffraction analyses. Isomorphous complexes 1 and 2 reveal polycatenated 2D+2D→3D framework based on an undulated (4,4)-sql layer. Complex 3 exhibits a new 4-fold interpenetrating 3D framework with the point symbol of 6{sup 6}. Molecular simulations were used to assess the potentials of the complexes for H{sub 2} storage application. Moreover, these coordination polymers exhibit blue fluorescent emission bands in the solid state at room temperature. - Graphical abstract: In this study, hydrothermal reactions of rigid 1,4-bis(imidazol-1-yl)benzene (dib) and 1,4-bis(imidazol-1-yl)-2,5-dimethylbenzene (dimb) with deprotonated thiophene-2,5-dicarboxylic acid (H{sub 2}tdc) in the presence of Zn(II) and Cd(II) salts in H{sub 2}O produced three new metal–organic frameworks. Isomorphous complexes 1 and 2 reveal polycatenated 2D+2D→3D framework based on an undulated (4,4)-sql layer. Complex 3 exhibits a new 4-fold interpenetrating 3D framework with the point symbol of 6{sup 6}. Molecular simulations were used to assess the potentials of the complexes for H{sub 2} storage application. These coordination polymers exhibit blue fluorescent emission bands in the solid state at room temperature. Display Omitted - Highlights: • Complexes 1 and 2 display polycatenated 2D+2D→3D framework. • Complex 3 exhibits a new 4-fold interpenetrating 3D framework. • Complex 1 adsorbs the highest amount of H{sub 2} at 100 bar and 298 K. • Complexes display blue fluorescent emission bands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Ionic conductivity and the formation of cubic CaH{sub 2} in the LiBH{sub 4}–Ca(BH{sub 4}){sub 2} composite

LiBH{sub 4}–Ca(BH{sub 4}){sub 2} composites were prepared by ball milling. Their crystal structures and phase composition were investigated using synchrotron X-ray diffraction and Rietveld refinement, and their ionic conductivity was measured using impedance spectroscopy. The materials were found to form a physical mixture. The composites were composed of α-Ca(BH{sub 4}){sub 2}, γ-Ca(BH{sub 4}){sub 2} and orthorhombic LiBH{sub 4}, and the relative phase quantities of the Ca(BH{sub 4}){sub 2} polymorphs varied significantly with LiBH{sub 4} content. The formation of small amounts of orthorhombic CaH{sub 2} and cubic CaH{sub 2} in a CaF{sub 2}-like structure was observed upon heat treatment. Concurrent formation of elemental boron may also occur. The ionic conductivity of the composites was measured using impedance spectroscopy, and was found to be lower than that of ball milled LiBH{sub 4}. Electronic band structure calculations indicate that cubic CaH{sub 2} with hydrogen defects is electronically conducting. Its formation along with the possible precipitation of boron therefore has an effect on the measured conductivity of the LiBH{sub 4}–Ca(BH{sub 4}){sub 2} composites and may increase the risk of an internal short-circuit in the cells. -- Graphical abstract: An Arrhenius plot of the ionic conductivity of the LiBH{sub 4}–Ca(BH{sub 4}){sub 2} composites (red, blue, green). The ionic conductivity of ball milled (gray) and non-milled (black) LiBH{sub 4} is shown for comparison. The filled symbols are measured during heating runs and the empty symbols are measured during subsequent cooling runs. The conductivity of the composites is in all cases higher during cooling, most probably due to the formation of an electronically conducting layer containing defect-rich cubic CaH{sub 2}. Such layer formation could eventually lead to a short circuit in the cell and reveals a general issue of chemical stability that should be attended to in the development of solid electrolyte materials. Highlights: • The LiBH{sub 4}–Ca(BH{sub 4}){sub 2} composite forms a physical mixture rather than a solid solution. • The formation of defect-rich, cubic CaH{sub 2} in a CaF{sub 2}-like structure is observed. • A new layer containing cubic CaH{sub 2} is conducting and may lead to a short-circuit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Syntheses, crystal structures, and characterization of three 1D, 2D and 3D complexes based on mixed multidentate N- and O-donor ligands

Three new 1D to 3D complexes, namely, ([Ni(btec)(Himb){sub 2}(H{sub 2}O){sub 2}]·6H{sub 2}O){sub n} (1), ([Cd(btec){sub 0.5}(imb)(H{sub 2}O)]·1.5H{sub 2}O){sub n} (2), and ([Zn(btec){sub 0.5}(imb)]·H{sub 2}O){sub n} (3) (H{sub 4}btec=1,2,4,5-benzenetetracarboxylic acid, imb=2-(1H-imidazol-1-methyl)-1H-benzimidazole) have been synthesized by adjusting the central metal ions. Single-crystal X-ray diffraction analyses reveal that complex 1 possesses a 1D chain structure which is further extended into the 3D supramolecular architecture via hydrogen bonds. Complex 2 features a 2D network with Schla¨fli symbol (5{sup 3}·6{sup 2}·7)(5{sup 2}·6{sup 4}). Complex 3 presents a 3D framework with a point symbol of (4·6{sup 4}·8)(4{sup 2}·6{sup 2}·8{sup 2}). Moreover, their IR spectra, PXRD patterns, thermogravimetric curves, and luminescent emissions were studied at room temperature. - Graphical abstract: Three new 1D to 3D complexes with different structural and topological motifs have been obtained by modifying the central metal ions. Additionally, their IR, TG analyses and fluorescent properties are also investigated. - Highlights: • Three complexes based on mixed multidentate N- and O-donor ligands. • The complexes are characterized by IR, luminescence and TGA techniques. • Benzenetetracarboxylates display different coordination modes in complexes 1–3. • Changing the metal ions can result in complexes with completely different structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Lanthanide coordination polymers: Synthesis, diverse structure and luminescence properties

The new semirigid exo-bidentate ligand incorporating furfurysalicylamide terminal groups, namely, 1,4-bis([(2′-furfurylaminoformyl)phenoxyl]methyl)-2,5-bismethylbenzene (L) was synthesized and used as building blocks for constructing lanthanide coordination polymers with luminescent properties. The series of lanthanide nitrate complexes have been characterized by elemental analysis, IR spectroscopy, and X-ray diffraction analysis. The semirigid ligand L, as a bridging ligand, reacts with lanthanide nitrates forming three distinct structure types: chiral noninterpenetrated two-dimensional (2D) honeycomblike (6,3) (hcb, Schläfli symbol 6{sup 3}, vertex symbol 6 6 6) topological network as type I, 1D zigzag chain as type II and 1D trapezoid ladder-like chain as type III. The structural diversities indicate that lanthanide contraction effect played significant roles in the structural self-assembled process. The luminescent properties of Eu{sup III}, Tb{sup III} and Dy{sup III} complexes are discussed in detail. Due to the good match between the lowest triplet state of the ligand and the resonant energy level of the lanthanide ion, the lanthanide ions in Eu{sup III}, Tb{sup III} and Dy{sup III} complexes can be efficiently sensitized by the ligand. - Graphical abstract: We present herein six lanthanide coordination polymers of a new semirigid exo-bidentate ligand which not only display diverse structures but also possess strong luminescence properties. - Highlights: • We present lanthanide coordination polymers of a new semirigid exo-bidentate ligand. • The lanthanide coordination polymers exhibit diverse structures. • The luminescent properties of Tb{sup III}, Eu{sup III} and Dy{sup III} complexes are discussed in detail.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

A set of alkali and alkaline-earth coordination polymers based on the ligand 2-(1H-benzotriazol-1-yl) acetic acid: Effects the radius of metal ions on structures and properties

Four new metal coordination complexes, namely, [Na(BTA)]{sub n} (1), [K{sub 2}(BTA){sub 2}(μ{sub 2}-H{sub 2}O)]{sub n} (2), and [M(BTA){sub 2}(H{sub 2}O){sub 2}]{sub n} (M=Ca(II) and Sr(II) for 3 and 4, respectively) [BTA=2-(1H-benzotriazol-1-yl) acetic anion], have been obtained under hydrothermal condition, by reacting the different alkali and alkaline-earth metal hydroxides with HBTA. Complexes 1–4 were structurally characterized by X-ray single-crystal diffraction, EA, IR, PXRD, and thermogravimetry analysis (TGA). These complexes display low-dimensional features displaying various two-dimensional (2D) and one-dimensional (1D) coordination motifs. Complex 1 displays a 2D layer with the thickness of 1.5 nm and possesses a topologic structure of a 11 nodal net with Schläfli symbol of (3{sup 18}). Complex 2 also shows a thick 2D sheet and its topologic structure is a 9 nodes with Schläfli symbol of (3{sup 11}×4{sup 2}). Complexes 3 and 4 possess a 1D linear chain and further stack via hydrogen bonding interactions to generate a three-dimensional supramolecular architecture. These results suggest that both the coordination preferences of the metal ions and the versatile nature of this flexible ligand play a critical role in the final structures. The luminescent spectra show strong emission intensities in complexes 1–4, which display violet photoluminescence. Additionally, ferroelectric, dielectric and nonlinear optic (NLO) second-harmonic generation (SHG) properties of 2 are discussed in detail. - Graphical abstract: A set of alkali and alkaline-earth metal coordination polymers were hydrothermally synthesized by 2-(1H-benzotriazol-1-yl)acetic acid, displaying interesting topologic motifs from two-dimension to one-dimension and specific physical properties. - Highlights: • Alkali and alkaline-earth metal coordination polymers have been obtained. • The ligand 2-(1H-benzotriazol-1-yl)acetic acid has been adopted. • The two-dimensional and one-dimensional structures have been observed. • The properties of second harmonic generation and ferroelectricity for complex 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 OSTI2016

Zinc(II) and Cadmium(II) coordination polymers constructed from phenylenediacetate ligands

ABSTRACT: A series of new coordination polymers {[Zn(μ-opda)(μ-bpa)]·2H_2O}{sub n} (1), [Zn(μ{sub 3}-ppda)(μ-bpa)]{sub n} (2), [Cd(μ{sub 3}-ppda)(μ-bpa)]{sub n} (3), [Cd(μ{sub 3}-mpda)(μ-bpa)]{sub n} (4) and [Cd(μ{sub 3}-mpda)(μ-bipy)]{sub n} (5), (o/m/ppda=1,2/1,3/1,4-phenylenediacetate, bpa=1,2-bi(4-pyridyl)ethane, bipy=4,4′-bipyridine) were synthesized. Their structures were characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffraction. Furthermore, the effect of metal sources (zinc acetate and zinc oxide) and acidity of the solution on the structure of the coordination polymers was discussed for complexes 1 and 5, respectively. The single-crystal X-ray crystallographic studies revealed that complexes 1, 3, 4 and 5 are uninodal (4)-connected 2D frameworks and display sql topology with the point symbol of (4{sup 4}.6{sup 2}). Complex 2 is 3D coordination polymer and exhibits pcu topology with the point symbol of (4{sup 12}.6{sup 3}). In addition, the luminescent properties and thermal behavior of all complexes were also investigated. - Graphical abstract: Scheme 1. Topologies of Coordination Polymers Reported in This Paper.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Two actinide-organic frameworks constructed by a tripodal flexible ligand: Occurrence of infinite ((UO{sub 2})O{sub 2}(OH){sub 3}){sub 4n} and hexanuclear (Th{sub 6}O{sub 4}(OH){sub 4}) motifs

Two new actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H{sub 3}tci) under hydrothermal condition. The combination of H{sub 3}tci and uranyl nitrate hexahydrate in aqueous solution leads to the isolation of [(UO{sub 2}){sub 2}(H{sub 2}O){sub 4}]{sub 0.5}(tci){sub 2}(UO{sub 2}){sub 4}(OH){sub 4}·18H{sub 2}O (1), which contains two distinct UO{sub 2}{sup 2+} coordination environments. Four uranyl cations, linked through μ{sub 3}-OH respectively, result in the edge-sharing ribbons. Then, the layer structure is constructed by U-O clusters linked through other eight-coordinated uranyl unions, giving rise to a porous structure in the space. Topological analysis reveals that complex 1 belongs to a (4, 8)-connected net with a schläfli symbol of (3{sup 4.}2{sup 6.}3){sub 2}(3{sup 4.}4{sup 6.}5{sup 6.}6{sup 8.}7{sup 3.}8). Th{sub 3}(tci){sub 2}O{sub 2}(OH){sub 2}(H{sub 2}O){sub 3}·12H{sub 2}O (2) generated by the reaction of H{sub 3}tci and thorium nitrate tetrahydrate, possesses nine-fold coodinated Th(IV) centers with a monocapped square antiprismatic geometry. The hexamers “Th{sub 6}O{sub 4}(OH){sub 4}” motifs are connected together by the carboxylate groups, showing a three-dimensional structures. Complex 2 takes on an 8-connected architecture and the point symbol is (4{sup 24.}6{sup 4}). - Graphical abstract: Two new 3D actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H3tci) and their topological structures were displayed. The infinite ((UO{sub 2})O{sub 2}(OH){sub 3}){sub 4n} and hexanuclear (Th{sub 6}O{sub 4}(OH){sub 4}) motifs were found in the title actinides networks.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A Deep Learning Based Framework to Identify Undocumented Orphaned Oil and Gas Wells from Historical Maps: A Case Study for California and Oklahoma

Undocumented Orphaned Wells (UOWs) are wells without an operator that have limited or no documentation with regulatory authorities. An estimated 310,000 to 800,000 UOWs exist in the United States (US), whose locations are largely unknown. These wells can potentially leak methane and other volatile organic compounds to the atmosphere, and contaminate groundwater. In this study, we developed a novel framework utilizing a state-of-the-art computer vision neural network model to identify the precise locations of potential UOWs. The U-Net model is trained to detect oil and gas well symbols in georeferenced historical topographic maps, and potential UOWs are identified as symbols that are further than 100 m from any documented well. A custom tool was developed to rapidly validate the potential UOW locations. We applied this framework to four counties in California and Oklahoma, leading to the discovery of 1301 potential UOWs across >40,000 km 2 . We confirmed the presence of 29 UOWs from satellite images and 15 UOWs from magnetic surveys in the field with a spatial accuracy on the order of 10 m. This framework can be scaled to identify potential UOWs across the US since the historical maps are available for the entire nation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

A General Sparse Tensor Framework for Electronic Structure Theory

Linear-scaling algorithms must be developed in order to extend the domain of applicability of electronic structure theory to molecules of any desired size. But, the increasing complexity of modern linear-scaling methods makes code development and maintenance a significant challenge. A major contributor to this difficulty is the lack of robust software abstractions for handling block-sparse tensor operations. We therefore report the development of a highly efficient symbolic block-sparse tensor library in order to provide access to high-level software constructs to treat such problems. Our implementation supports arbitrary multi-dimensional sparsity in all input and output tensors. We then avoid cumbersome machine-generated code by implementing all functionality as a high-level symbolic C++ language library and demonstrate that our implementation attains very high performance for linear-scaling sparse tensor contractions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

High-Temperature Thermoelectric Properties of the Solid-Solution Zintl Phase Eu 11 Cd 6 Sb 12-x As x (x < 3)

Zintl phases are compounds that have shown promise for thermoelectric applications. The title solid–solution Zintl compounds were prepared from the elements as single crystals using a tin flux for compositions x = 0, 1, 2, and 3. Eu 11 Cd 6 Sb 12–x As x (x < 3) crystallize isostructurally in the centrosymmetric monoclinic space group C2/m (no. 12, Z = 2) as the Sr 11 Cd 6 Sb 12 structure type (Pearson symbol mC58). Efforts to make the As compositions for x exceeding ~3 resulted in structures other than the Sr 11 Cd 6 Sb 12 structure type. Single-crystal X-ray diffraction indicates that As does not randomly substitute for Sb in the structure but is site specific for each composition. The amount of As determined by structural refinement was verified by electron microprobe analysis. Electronic structures and energies calculated for various model structures of Eu 11 Cd 6 Sb 10 As 2 (x = 2) indicated that the preferred As substitution pattern involves a mixture of three of the six pnicogen sites in the asymmetric unit. In addition, As substitution at the Pn4 site opens an energy gap at the Fermi level, whereas substitution at the other five pnicogen sites remains semimetallic with a pseudo gap. Thermoelectric properties of these compounds were measured on hot-pressed, fully densified pellets. Samples show exceptionally low lattice thermal conductivities from room temperature to 775 K: 0.78–0.49 W/mK for x = 0; 0.72–0.53 W/mK for x = 1; and 0.70–0.56 W/mK for x = 2. Eu 11 Cd 6 Sb 12 shows a high p-type Seebeck coefficient (from +118 to 153 μ V/K) but also high electrical resistivity (6.8 to 12.8 mΩ·cm). The value of zT reaches 0.23 at 774 K. The properties of Eu 11 Cd 6 Sb 12–x As x are interpreted in discussion with the As site substitution.

Kazem, Nasrin↗