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All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Niobium-bearing arsenides and germanides from elemental mixtures not involving niobium: a new twist to an old problem in solid-state synthesis

Three isostructural transition-metal arsenides and germanides, namely niobium nickel arsenide, Nb 0.92(1) NiAs, niobium cobalt arsenide, NbCoAs, and niobium nickel germanide, NbNiGe, were obtained as inadvertent side products of high-temperature reactions in sealed niobium containers. In addition to reporting for the very first time the structures of the title compounds, refined from single-crystal X-ray diffraction data, this article also serves as a reminder that niobium containers may not be suitable for the synthesis of ternary arsenides and germanides by traditional high-temperature reactions. Synthetic work involving alkali or alkaline-earth metals, transition or early post-transition metals, and elements from groups 14 or 15 under such conditions may yield Nb-containing products, which at times could be the major products of such reactions.

Chemistry↗
DOE OSTI2018

Crystal structure of the layered arsenide Rb 3 Cu 3 As 2

The crystal structure of a new arsenide, Rb 3 Cu 3 As 2 (trirubidium tricopper diarsenide), has been established from single-crystal X-ray diffraction data. This compound crystallizes in the K 3 Cu 3 P 2 type, with layers of interlinked CuAs 2 units. The partitioning of the available valence electrons yields the charge-balanced composition (Rb + ) 3 (Cu + ) 3 (As 3– ) 2 , placing this phase in a broad field of transition-metal-containing Zintl phases. First-principles calculations confirm a semiconducting ground state, in accordance with electron-counting considerations. Chemical bonding analysis reveals strong covalent Cu—As bonds and ionic Rb...As interactions. In addition, a weak attraction is found between the Cu atoms, possibly pointing toward cuprophilic interactions.

Chemistry↗
DOE OSTI2020

Fourfold alkyl wrapping of a copper(II) porphyrin thwarts macrocycle π–π stacking in a compact supramolecular package

Porphyrins are valuable constituents in optoelectronic, catalytic, and other applications, yet control of intermolecular π–π stacking is invariably essential to attain the desired properties. Superstructures built onto the porphyrin, often via meso -aryl groups, can afford facial encumbrance that suppresses π–π stacking, although some molecular designs have provided insufficient facial coverage and many have entailed cumbersome syntheses. In this study, a copper(II) porphyrin bearing four meso substituents, namely, {10,20-bis[2,6-bis(octyloxy)phenyl]-5,15-dibromoporphinato}copper(II), [Cu(C 64 H 82 Br 2 N 4 O 4 )], was prepared by metalation of the corresponding free-base porphyrin and was characterized by single-crystal X-ray diffraction. The crystal structure reveals a dihedral angle of 111.1 (2)° for the plane of the meso -aryl group relative to the plane of the porphyrin, with both aryl groups tilted in the same direction. Each of the four octyloxy groups exhibits a gauche conformation for the –OCH 2 CH 2 – unit but is extended with four or five anti (–CH 2 CH 2 –/H) conformations thereafter, causing each octyl group to span the dimension of the macrocycle. In a global frame of reference where the two Br atoms define the north/south poles and the two aryl groups are at antipodes on the equator, two octyl groups of one aryl unit project over the northern hemisphere (covering pyrroles A and B ), whereas those of the other aryl unit project over the southern hemisphere (covering pyrroles C and D ). Together, the four octyl groups ensheath the two faces of the porphyrin in a self-wrapped assembly. The closest approach of the Cu atom to an octyl methylene C atom (position 6) is 3.5817 (18) Å, the mean separations of neighboring porphyrin planes are 8.059 (4) and 4.693 (8) Å along the a and c axes, respectively, and the center-to-center distances between the Cu atoms of neighboring porphyrins are 10.2725 (4), 12.2540 (6), and 12.7472 (6) Å along the a , b , and c axes, respectively. The Hirshfeld surface analysis and two-dimensional (2D) fingerprint plots provide information concerning contact interactions in the supramolecular assembly of the solid crystal.

Chemistry↗
DOE OSTI2020

Synthesis, structural characterization, and electronic structure of the novel Zintl phase Ba 2 ZnP 2

The novel Zintl phase dibarium zinc diphosphide (Ba 2 ZnP 2 ) was synthesized for the first time. This was accom­plished using the Pb flux technique, which allowed for the growth of crystals of adequate size for structural determination via single-crystal X-ray diffraction methods. The Ba 2 ZnP 2 com­pound was determined to crystallize in a body-centered ortho­rhom­bic space group, Ibam (No. 72). Formally, this crystallographic arrangement belongs to the K 2 SiP 2 structure type. Therefore, the structure can be best described as infinite [ZnP 2 ] 4– polyanionic chains with divalent Ba 2+ cations located between the chains. All valence electrons are partitioned, which conforms to the Zintl–Klemm concept and suggests that Ba 2 ZnP 2 is a valence-precise com­position. In conclusion, the electronic band structure of this new com­pound, com­puted with the aid of the TB–LMTO–ASA code, shows that Ba 2 ZnP 2 is an intrinsic semiconductor with a band gap of ca 0.6 eV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Step-stool conformation of a cyclic Schiff base derived from ethylenediamine and heptane-2,4,6-trione: evidence for partial hydrolysis in metal coordination

A Schiff base derived from ethylenediamine and heptane-2,4,6-trione, namely, 5,9,14,18-tetramethyl-1,4,10,13-tetraazacyclooctadeca-5,8,14,17-tetraene-7,16- dione (C 18 H 28 N 4 O 2 ), abbreviated H 4 daaden, was prepared and characterized for the first time by single-crystal X-ray diffraction. The atoms of the Schiff base occupy two different planes and thus the molecule is essentially nonplanar. An axis running through the C–C atoms of the ethylenediamine groups separate the two planes and these two planes are connected by bridging ethylene groups showing an angle of 117.34 (8)°. As a result, the side view of the molecule shows a ‘step-stool’ conformation. The nonplanar nature of the Schiff base plays an important role in metal coordination, which leads to partial hydrolysis of the ring structure

crystal structure↗
DOE OSTI2020

The crystal structure of TlMgCl 3 from 290 K to 725 K

The title compound, thallium magnesium trichloride, has been identified as a scintillator with both moderate gamma-stopping power and moderate light yield. Knowledge of its crystal structure is needed for further development. This work determines the crystal structure of TlMgCl 3 to be hexa­gonal P6 3 /mmc (No. 194) and isostructural with RbMgCl 3 , contrary to previously reported data. This structure was obtained by single-crystal X-ray diffraction and was further confirmed by neutron diffraction measurements. Extending neutron diffraction measurements to high temperature, the data show that TlMgCl 3 maintains this crystal structure from 290 K up through 725 K, approaching the melting point of 770 K. Anisotropic thermal expansion coefficients increase over this temperature range, from 31 to 38 × 10 –6 K –1 along the a axis and from 19 to 34 × 10 –6 K –1 along the c axis.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Structural and spectral dynamics of single-crystalline Ruddlesden-Popper phase halide perovskite blue light-emitting diodes

Achieving perovskite-based high–color purity blue-emitting light-emitting diodes (LEDs) is still challenging. Here, we report successful synthesis of a series of blue-emissive two-dimensional Ruddlesden-Popper phase single crystals and their high–color purity blue-emitting LED demonstrations. Although this approach successfully achieves a series of bandgap emissions based on the different layer thicknesses, it still suffers from a conventional temperature-induced device degradation mechanism during high-voltage operations. To understand the underlying mechanism, we further elucidate temperature-induced device degradation by investigating the crystal structural and spectral evolution dynamics via in situ temperature-dependent single-crystal x-ray diffraction, photoluminescence (PL) characterization, and density functional theory calculation. The PL peak becomes asymmetrically broadened with a marked intensity decay, as temperature increases owing to [PbBr 6 ] 4- octahedra tilting and the organic chain disordering, which results in bandgap decrease. This study indicates that careful heat management under LED operation is a key factor to maintain the sharp and intense emission.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Diverse high-pressure chemistry in Y-NH 3 BH 3 and Y–paraffin oil systems

The yttrium-hydrogen system has gained attention because of near-ambient temperature superconductivity reports in yttrium hydrides at high pressures. We conducted a study using synchrotron single-crystal x-ray diffraction (SCXRD) at 87 to 171 GPa, resulting in the discovery of known (two YH3 phases) and five previously unknown yttrium hydrides. These were synthesized in diamond anvil cells by laser heating yttrium with hydrogen-rich precursors—ammonia borane or paraffin oil. The arrangements of yttrium atoms in the crystal structures of new phases were determined on the basis of SCXRD, and the hydrogen content estimations based on empirical relations and ab initio calculations revealed the following compounds: Y 3 H 11 , Y 2 H 9 , Y 4 H 23 , Y 13 H 75 , and Y 4 H 25 . The study also uncovered a carbide (YC 2 ) and two yttrium allotropes. Complex phase diversity, variable hydrogen content in yttrium hydrides, and their metallic nature, as revealed by ab initio calculations, underline the challenges in identifying superconducting phases and understanding electronic transitions in high-pressure synthesized materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Berkelium–carbon bonding in a tetravalent berkelocene

Interest in actinide–carbon bonds has persisted since actinide organometallics were first investigated for applications in isotope separation during the Manhattan Project. Transplutonium organometallics are rarely isolated and structurally characterized, likely owing to limited isotope inventories, a scarcity of suitable laboratory infrastructure, and intrinsic difficulties with the anaerobic conditions required. In this paper, we report the discovery of an organometallic “berkelocene” complex prepared from 0.3 milligrams of berkelium-249. Single-crystal x-ray diffraction shows a tetravalent berkelium ion between two substituted cyclooctatetraene ligands, resulting in the formation of berkelium–carbon bonds. The coordination in berkelocene resembles that of uranocene, and calculations show that the berkelium 5f orbitals engage in covalent overlap with the δ-symmetry orbitals of the cyclooctatetraenide ligand π system. Charge transfer from the ligands is diminished relative to uranocene and other actinocenes, which maximizes contributions from the stable, half-filled 5f 7 configuration of tetravalent berkelium.

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

Iron-rich bustamite from Broken Hill, Australia: The crystal structure and cation-ordering features

A specimen of iron-rich bustamite from the Broken Hill deposit (Australia) has been studied by single-crystal X-ray diffraction and by Mössbauer and IR spectroscopy. The triclinic unit-cell parameters are as follows: a = 7.1301(4) Å, b = 7.6940(3) Å, c = 7.7345(4) Å, α = 79.352(4)°, β = 62.951(6)°, γ = 76.149(3)°, V = 365.49(3) Å{sup 3}, sp. gr. P1̄. The structure is solved by direct methods and refined to R = 5.22% based on 7298 reflections with |F| > 4σ(F). The mineral under study is similar in composition and structure to the Fe-rich bustamite described earlier. It is found that all iron atoms are in the divalent state and occupy the M1 and M3 sites in a ratio of 33: 67. The idealized formula of iron-rich bustamite from Broken Hill (Z = 1) is Mn{sub 2}Ca{sub 2}(Fe,Mn)Ca[Si{sub 3}O{sub 9}]{sub 2}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

The crystal structure and microtwinning of ferro-pedrizite, a new lithium amphibole

The structure of ferro-pedrizite—a new lithium mineral of the amphibole supergroup—has been studied by single-crystal X-ray diffraction. Fe{sup 2+} ions dominate over Mg in the chemical composition of this mineral. The parameters of the monoclinic unit cell are a = 9.3716(4) Å, b = 17.649(1) Å, c = 5.2800(6) Å, and β = 102.22(1)°. The experimental set of intensities contains a large number of significant reflections (~10%), which violate the Clattice. Consideration of pseudomerohedral twinning (matrix [1 0 0/01̄0/–3/4 01̄]) allowed us to solve and refine the structure within the sp. gr. C2/m to the final value R = 3.9% in the anisotropic approximation of atomic displacements using 4843I > 2σ(I). The twin components are found to be 0.681(3)/0.319(3). Twinning has been revealed for the first time in amphiboles of the pedrizite family. The idealized formula of ferro-pedrizite (Z = 2) is determined as NaLi{sub 2}(Fe{sub 2}{sup 2+}Al{sub 2}Li)[Si{sub 8}O{sub 22}](OH){sub 2}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Synthesis, crystal structure refinement, and nonlinear-optical properties of CaB{sub 3}O{sub 5}(OH): Comparative crystal chemistry of calcium triborates

Calcium triborate CaB{sub 3}O5(OH) obtained by hydrothermal synthesis in the Ca(OH){sub 2}–H{sub 3}BO{sub 3}–Na{sub 2}CO{sub 3}–KCl system is studied by single-crystal X-ray diffraction. The parameters of the orthorhombic unit cell are as follows: a = 13.490(1), b = 6.9576(3), and c = 4.3930(2) Å; V = 412.32(3) Å{sup 3} and space group Pna2{sub 1}. The structure is refined in the anisotropic approximation of the atomic displacement parameters to R = 4.28% using 972 vertical bar F vertical bar > 4σ(F). It is confirmed that the crystal structure of Ca triborate CaB{sub 3}O{sub 5}(OH) is identical to that described earlier. The hydrogen atom is localized. An SHG signal stronger than that of the quartz standard is registered. The phase transition of calcium triborate into calciborite is found on heating. The comparative crystal-chemical analysis of a series of borates with the general chemical formula 2CaO · 3B{sub 2}O{sub 3} · nH{sub 2}O (n = 0–13) with the constant CaO: B{sub 2}O{sub 3}= 2: 3 ratio and variable content of water is performed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Crystal structure and genesis of the hydrated analog of rastsvetaevite

The crystal structure of the hydrated analog of the mineral rastsvetaevite (tentatively called “hydrorastsvetaevite”), which was found by A.P. Khomyakov in ultraagpaitic pegmatites at the Rasvumchorr Mountain of the Khibiny alkaline massif (Kola Peninsula), has been determined by single crystal X-ray diffraction. The trigonal unit-cell parameters are as follows: a = 14.2812(2) Å, c = 60.533(5) Å, V = 10691.54(3) Å{sup 3}, sp. gr. R3m. The structure was refined to R = 5.9% in the isotropic and anisotropic approximation of atomic displacement parameters based on 2068 ref lections with |F| > 3σ(F). “Hydrorastsvetaevite” is on the whole analogous to other 24-layer representatives of the eudialyte group (called “megaeudialytes”), but is characterized by a high potassium content and is distinguished from other potassium-rich minerals (rastsvetaevite, davinciite, and andrianovite) by low sodium and alkaline-earth metal content, as well as by a high degree of hydration accompanied by the insertion of H{sub 3}O groups, which partially or completely replace large cations. The idealized formula of “hydrorastsvetaevite” (Z = 3) is (Na{sub 11}(H{sub 3}O){sub 11}K{sub 6}(H{sub 2}O){sub 1.5}Sr)Ca{sub 12}Fe{sub 3}Na{sub 2}MnZr{sub 6}Si{sub 52}O{sub 144}(OH){sub 4.5}C{sub l3.5}(H{sub 2}O){sub 0.5}. In alkaline pegmatites, “hydrorastsvetaevite” occurs as a secondary mineral developed from the original rastsvetaevite through decationation and hydration. The characteristic features of the genesis of eudialyte-group minerals containing potassium as a species-forming cation are discussed in terms of the concept of transformational mineral species.an]Mis||Original Russian Text © R.K. Rastsvetaeva, S.M. Aksenov, K.A. Rozenberg, 2015, published in Kristallografiya, 2015, Vol. 60, No. 6, pp. 897–905.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Synthesis and characterization of a cadmium bipyridinium compound (CdCl{sub 4})(N,N'-dimethyl-2,2'-bipyridinium)

A cadmium bipyridinium compound (CdCl{sub 4})(N,N'-dimethyl-2,2'-bipyridinium), in which the (N,N'-dimethyl-2,2'-bipyridinium){sup 2+} moieties were generated in situ, has been prepared via solvothermal reactions and structurally characterized with single crystal X-ray diffraction method. Fluorescence measurement revealed a broad and strong emission band in the blue region.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Crystal structures and intermolecular interactions of two novel antioxidant triazolyl-benzimidazole compounds

The crystal structures of 5-(2-(p-chlorophenylbenzimidazol-1-yl-methyl)-4-(3-fluorophenyl)-2, 4-dihydro-[1,2,4]-triazole-3-thione (G6C) and 5-(2-(p-chlorophenylbenzimidazol-1-yl-methyl)-4-(2-methylphenyl)-2, 4-dihydro-[1,2,4]-triazole-3-thione (G4C) have been determined by single-crystal X-ray diffraction. Benzimidazole ring systems in both molecules are planar. The triazole part is almost perpendicular to the phenyl and the benzimidazole parts of the molecules in order to avoid steric interactions between the rings. The crystal structures are stabilized by intermolecular hydrogen bonds between the amino group of the triazole and the nitrogen atom of benzimidazole of a neighboring molecule.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Organic compounds containing methoxy and cyanoacrylic acid: Synthesis, characterization, crystal structures, and theoretical studies

Metal-free organic compounds 24-SC ((E)-2-cyano-3-(2,4-dimethoxyphenyl)acrylic acid) and 34-SC ((E)-2-cyano-3-(3,4-dimethoxyphenyl)acrylic acid), containing methoxy groups as a donor and the acrylic acid as an acceptor were synthesized and characterized by CHN, FT-IR, UV-Vis, {sup 1}H-NMR and single crystal X-ray diffraction and used as photosensitizers for the application of dye-sensitized solar cells (DSSC). The sensitizing characteristics of them were evaluated. Both compounds contain the natural molecule, its anionic form and the piperidinium cation and they differ by number of these molecules in the asymmetric unit. To get further insight into the effect of molecular structure on the performance of DSSC, their geometry and energies of HOMO and LUMO were optimized by density functional theory calculation at the B3LYP/6-31G(d) level with Gaussian 03. Overall conversion efficiencies of 0.78 under full sunlight irradiation are obtained for DSSCs based on the new metal-free organic dyes 24-SC and 34-SC.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗