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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.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Single-Crystal-to-Single-Crystal Post-Synthetic Modifications

Chalcogenides are the cornerstone of the semiconductor and thermoelectric industries and are up-and-coming materials for superconductors, catalysis, and battery applications. Challenges in synthesizing those materials emerge from the chalcogen's volatility and the tendencies of chalcogenides to react with even trace quantities of oxygen. Many techniques have been applied to the growth of chalcogenide single crystals, which are convenient for structure determinations and intrinsic property measurements. One of the recent advances in chalcogenide chemistry is the intriguing single-crystal-to-single-crystal (SCSC) transformation, leading to new metastable compositions. Post-synthetic transformations are well-known and studied for chalcogenide powders; however, examples of post-synthetic conversions that retain single crystallinity are rare. To date, the scope of SCSC reactions includes (de)intercalation in the layered compositions and ion exchange in open-framework materials, salt-inclusion chalcogenides, and layered structures. This poster will discuss the successful examples of SCSC modifications monitored by single-crystal X-ray diffraction (SC-XRD), emphasizing how post-synthetic transformations affect materials' properties.

chalcogenide↗
DOE OSTI2023

Single‐Crystal to Single‐Crystal Transformations: Stepwise CO 2 Insertions into Bridging Hydrides of [(NHC)CuH] 2 Complexes

Abstract Mechanistic studies of substrate insertion into dimeric [(NHC)CuH] 2 (NHC=N‐heterocyclic carbene) complexes with two bridging hydrides have been shown to require dimer dissociation to generate transient, highly reactive (NHC)Cu−H monomers in solution. Using single‐crystal to single‐crystal (SC‐SC) transformations, we discovered a new pathway of stepwise insertion of CO 2 into [(NHC)CuH] 2 without complete dissociation of the dimer. The first CO 2 insertion into dimeric [(IPr*OMe)CuH] 2 (IPr*OMe=N,N′‐bis(2,6‐bis(diphenylmethyl)‐4‐methoxy‐phenyl)imidazole‐2‐ylidene) produced a dicopper formate hydride [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐H). A second CO 2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐1,1‐O 2 CH), containing two different bonding modes of the bridging formate. These dicopper formate complexes are inaccessible from solution reactions since the dicopper core cleanly ruptures to monomeric complexes when dissolved in a solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Single‐Crystal to Single‐Crystal Transformations: Stepwise CO 2 Insertions into Bridging Hydrides of [(NHC)CuH] 2 Complexes

Abstract Mechanistic studies of substrate insertion into dimeric [(NHC)CuH] 2 (NHC=N‐heterocyclic carbene) complexes with two bridging hydrides have been shown to require dimer dissociation to generate transient, highly reactive (NHC)Cu−H monomers in solution. Using single‐crystal to single‐crystal (SC‐SC) transformations, we discovered a new pathway of stepwise insertion of CO 2 into [(NHC)CuH] 2 without complete dissociation of the dimer. The first CO 2 insertion into dimeric [(IPr*OMe)CuH] 2 (IPr*OMe=N,N′‐bis(2,6‐bis(diphenylmethyl)‐4‐methoxy‐phenyl)imidazole‐2‐ylidene) produced a dicopper formate hydride [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐H). A second CO 2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐1,1‐O 2 CH), containing two different bonding modes of the bridging formate. These dicopper formate complexes are inaccessible from solution reactions since the dicopper core cleanly ruptures to monomeric complexes when dissolved in a solvent.

Patrick, Evan A.↗
DOE OSTI2025

4f-orbital covalency enables a single-crystal-to-single-crystal ring-opening isomerization in a CeIV–cyclopropenyl complex

Metal–ligand bonding interactions for f-element compounds are typically highly polarized with only minor covalent character. Whereas the 5d/6d orbitals are known to be chemically accessible for dative bonding, recent quantum chemical and spectroscopic analyses have indicated appreciable 4f/5f-orbital involvement in certain metal–ligand bonds. However, 4f-orbital covalency has not been compellingly linked to distinctive modes of chemical reactivity via rigorous comparative study and mechanistic investigation. Here a series of MIV–cyclopropenyl complexes (M = Ti, Zr, Ce, Hf, Th) are described, wherein the cerium congener exhibits a 4f-covalent Ce=Cα interaction, causing a ring-opening isomerization reaction through a single-crystal-to-single-crystal transformation. The results provide evidence for 4f-orbital covalency by demonstrating its expression in the reactivity of an f-element complex within an isostructural series of tetravalent d- and f-block metal complexes. They also provide new directions for the study of orbital covalency effects of molecular compounds in solid-state chemical transformations.

Vincenzini, Brett D↗
DOE OSTI2015

Single-crystal-to-single-crystal metalation of a metal-organic framework: A route toward structurally well-defined catalysts

Metal–organic frameworks featuring ligands with open chelating groups are versatile platforms for the preparation of a diverse set of heterogeneous catalysts through postsynthetic metalation. The crystalline nature of these materials allows them to be characterized via X-ray diffraction, which provides valuable insight into the structure of the metal sites that facilitate catalysis. A highly porous and thermally robust zirconium-based metal–organic framework, Zr 6 O 4 (OH) 4 (bpydc) 6 (bpydc 2– = 2,2'-bipyridne-5,5'-dicarboxylate), bears open bipyridine sites that readily react with a variety of solution- and gas-phase metal sources to form the corresponding metalated frameworks. Remarkably, Zr 6 O 4 (OH) 4 (bpydc) 6 undergoes a single-crystal-to-single-crystal transformation upon metalation that involves a change in space group from $Fm\bar{3}m$ to $Pa\bar{3}m$. This structural transformation leads to an ordering of the metalated linkers within the framework, allowing structural characterization of the resulting metal complexes. Furthermore, Zr 6 O 4 (OH) 4 (bpydc) 6 yields an active heterogeneous catalyst for arene C–H borylation when metalated with [Ir(COD) 2 ]BF 4 (COD = 1,5-cyclooctadiene). These results highlight the unique potential of metal–organic frameworks as a class of heterogeneous catalysts that allow unparalleled structural characterization and control over their active sites.

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

Brownmillerite Ca 2 Co 2 O 5 : Synthesis, Stability, and Re-entrant Single Crystal to Single Crystal Structural Transitions

We synthesized Ca 2 Co 2 O 5 in the brownmillerite form using a high-pressure optical-image floating zone furnace, and single crystals with dimensions up to 1.4×0.8×0.5 mm 3 were obtained. At room temperature, Ca 2 Co 2 O 5 crystallizes as a fully ordered brownmillerite variant in the orthorhombic space group Pcmb (No. 57) with unit cell parameters a=5.28960(10) Å, b=14.9240(2) Å, and c=10.9547(2) Å. Furthermore, with decreasing temperature, it undergoes re-entrant sequence of first-order structural phase transitions (Pcmb→ P2/c11→ P121/m1→ Pcmb) that is unprecedented among brownmillerites, broadening the family of space groups available to these materials and challenging current approaches for sorting the myriad variants of brownmillerite structures. Magnetic susceptibility data indicate antiferromagnetic ordering in Ca 2 Co 2 O 5 occurs near 240 K, corroborated by neutron powder diffraction. Below 140 K, Ca 2 Co 2 O 5 shows a weak ferromagnetic component directed primarily along the b axis, and it also exhibits thermal and magnetic history dependence in magnetization.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Single-Crystal Polycationic Polymers Obtained by Single-Crystal-to-Single-Crystal Photopolymerization

The efficient preparation of single-crystalline ionic polymers and fundamental understanding of their structure–property relationships at the molecular level remains a challenge in chemistry and materials science. Herein, we observe the single-crystal structure of a highly ordered polycationic polymer (polyelectrolyte) and its proton conductivity. The polyelectrolyte single crystals can be prepared on a gram-scale in quantitative yield, by taking advantage of an ultraviolet/sunlight-induced topochemical polymerization, from a tricationic monomer—a self-complementary building block possessing a preorganized conformation. A single-crystal-to-single-crystal photopolymerization was revealed unambiguously by in situ single-crystal X-ray diffraction analysis, which was also employed to follow the progression of molecular structure from the monomer, to a partially polymerized intermediate, and, finally, to the polymer itself. Collinear polymer chains are held together tightly by multiple Coulombic interactions involving counterions to form two-dimensional lamellar sheets (1 nm in height) with sub-nanometer pores (5 Å). The polymer is extremely stable under 254 nm light irradiation and high temperature (above 500 K). The extraordinary mechanical strength and environmental stability—in combination with its impressive proton conductivity (~3 × 10 –4 S cm –1 )—endow the polymer with potential applications as a robust proton-conducting material. By marrying supramolecular chemistry with macromolecular science, the outcome represents a major step toward the controlled synthesis of single-crystalline polyelectrolyte materials with perfect tacticity.

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

Growth and structure of K{sub 2}Ni{sub x}Co{sub (1–x)}(SO{sub 4}){sub 2} · 6H{sub 2}O single crystals

Single crystals of the K{sub 2}Ni{sub x}Co{sub (1–x)}(SO{sub 4}){sub 2} · 6H{sub 2}O composition are grown by spontaneous flux crystallization. More exact chemical formulas of the single crystals are determined based on the diffraction data as K{sub 2}Co(SO{sub 4}){sub 2} · 6H{sub 2}O (I), K{sub 2}(Co{sub 0.657}Ni{sub 0.343})(SO{sub 4}){sub 2} · 6H{sub 2}O (II), K{sub 2}(Co{sub 0.226}Ni{sub 0.774})(SO{sub 4}){sub 2} · 6H{sub 2}O (III), K{sub 2}(Co{sub 0.216}Ni{sub 0.784})(SO{sub 4}){sub 2} · 6H{sub 2}O (IV), and K{sub 2}Ni(SO{sub 4}){sub 2} · 6H{sub 2}O (V). The substitution of nickel atoms for cobalt atoms in structure I results in a shortening of all (Co,Ni)–O interatomic distances. With increasing Ni concentration, the (Co,Ni)–O2 distance shortens to a lesser degree than the (Co,Ni)–O1 and (Co,Ni)–O3 distances and, as a consequence, the distortion of (Co,Ni)O{sub 6} octahedra decreases. NiO{sub 6} polyhedra are less distorted than CoO{sub 6} octahedra. The analysis of difference syntheses of electron density shows that the number of uninterpretable peaks on the maps of mixed crystals II, III, and IV, as well as on the map of K{sub 2}Co(SO{sub 4}){sub 2} · 6H{sub 2}O, is larger with respect to those of structure K{sub 2}Ni(SO{sub 4}){sub 2} · 6H{sub 2}O.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Antiferromagnetism in EuCu 2 As 2 and EuCu 1.82 Sb 2 single crystals

Single crystals of EuCu 2 As 2 and EuCu 2 Sb 2 were grown from CuAs and CuSb self-flux, respectively. The crystallographic, magnetic, thermal, and electronic transport properties of the single crystals were investigated by room-temperature x-ray diffraction (XRD), magnetic susceptibility χ versus temperature T, isothermal magnetization M versus magnetic field H, specific heat C p (T), and electrical resistivity ρ(T) measurements. EuCu 2 As 2 crystallizes in the body-centered tetragonal ThCr 2 Si 2 -type structure (space group I4/mmm), whereas EuCu 2 Sb 2 crystallizes in the related primitive tetragonal CaBe 2 Ge 2 -type structure (space group P4/nmm). The energy-dispersive x-ray spectroscopy and XRD data for the EuCu 2 Sb 2 crystals showed the presence of vacancies on the Cu sites, yielding the actual composition EuCu 1.82 Sb 2 . The ρ(T) and C p (T) data reveal metallic character for both EuCu 2 As 2 and EuCu 1.82 Sb 2 . Antiferromagnetic (AFM) ordering is indicated from the χ(T),C p (T), and ρ(T) data for both EuCu 2 As 2 (T N = 17.5 K) and EuCu 1.82 Sb 2 (T N = 5.1 K). In EuCu 1.82 Sb 2 , the ordered-state χ(T) and M(H) data suggest either a collinear A-type AFM ordering of Eu +2 spins S = 7/2 or a planar noncollinear AFM structure, with the ordered moments oriented in the tetragonal ab plane in either case. This ordered-moment orientation for the A-type AFM is consistent with calculations with magnetic dipole interactions. As a result, the anisotropic χ(T) and isothermal M(H) data for EuCu 2 As 2 , also containing Eu +2 spins S = 7/2, strongly deviate from the predictions of molecular field theory for collinear AFM ordering and the AFM structure appears to be both noncollinear and noncoplanar.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Growth and Characterization of Ce- Substituted Nd 2 Fe 14 11 B Single Crystals

Single crystals of (Nd 1-x Ce x ) 2 Fe 14 B are grown out of Fe-(Nd,Ce) flux. Chemical and structural analysis of the crystals indicates that (Nd 1-x Ce x ) 2 Fe 14 B forms a solid solution until at least x = 0.38 with a Vegard-like variation of the lattice constants with x. Refinements of single crystal neutron diffraction data indicate that Ce has a slight site preference (7:3) for the 4g rare earth site over the 4f site. Furthermore, magnetization measurements show that for x = 0.38 the saturation magnetization at 400 K, a temperature important to applications, falls from 29.8 for the parent Nd 2 Fe 14 B to 27.6 μ B /f.u., the anisotropy field decreases from 5.5 T to 4.7 T, and the Curie temperature decreases from 586 to 543 K. First principles calculations carried out within density functional theory are used to explain the decrease in magnetic properties due to Ce substitution. Although the presence of the lower-cost and more abundant Ce slightly affects these important magnetic characteristics, this decrease is not large enough to affect a multitude of applications. Ce-substituted Nd 2 Fe 14 B is therefore a potential high-performance permanent magnet material with substantially reduced Nd content.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Structural study of quasi-one-dimensional vanadium pyroxene LiVSi{sub 2}O{sub 6} single crystals

Single crystals of quasi-one-dimensional vanadium pyroxene LiVSi{sub 2}O{sub 6} were synthesized and the crystal structures at 293 K and 113 K were studied using X-ray diffraction experiments. We found a structural phase transition from the room-temperature crystal structure with space group C2/c to a low-temperature structure with space group P2{sub 1}/c, resulting from a rotational displacement of SiO{sub 4} tetrahedra. The temperature dependence of magnetic susceptibility shows a broad maximum around 116 K, suggesting an opening of the Haldane gap expected for one-dimensional antiferromagnets with S=1. However, an antiferromagnetic long-range order was developed below 24 K, probably caused by a weak inter-chain magnetic coupling in the compound. - Graphical abstract: Low temperature crystal structure of LiVSi{sub 2}O{sub 6} and an orbital arrangement within the V-O zig-zag chain along the c-axis. - Highlights: • A low temperature structure of LiVSi{sub 2}O{sub 6} was determined by single crystal X-ray diffraction measurements. • The origin of the structural transition is a rotational displacement of SiO{sub 4} tetrahedra. • The uniform orbital overlap in the V-O zigzag chain makes the system a quasi one-dimensional antiferromagnet.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Possible Mott transition in layered Sr 2 Mn 3 As 2 O 2 single crystals

Single crystals of Sr 2 Mn 3 As 2 O 2 have been grown for the first time, for which we show a possible layer-selective Mott insulator behavior. This compound stands out as a hybrid structure of MnO 2 and MnAs layers, analogously to the active CuO 2 and FeAs layers, respectively, in the cuprate and iron-based high-temperature superconductors. Electrical transport, neutron diffraction measurements, together with density functional theory calculations on Sr 2 Mn 3 As 2 O 2 single crystals converge toward a picture of independent magnetic order at T 1 ~ 79 K and T 2 ~ 360 K for the two Mn sublattices, with insulating behavior at odds with the metallic behavior predicted by calculations. Furthermore, our inelastic neutron-scattering studies of spin-wave dispersions for the Mn(1) sublattice reveal an effective magnetic exchange coupling of SJ ~ 3.7 meV. This is much smaller than those for the Mn(2) sublattice.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Structure of Cs{sub 4}(HSO{sub 4}){sub 3}(H{sub 2}PO{sub 4}) single crystals

Single crystals of Cs{sub 4}(HSO{sub 4}){sub 3}(H{sub 2}PO{sub 4}) are synthesized and studied for the first time. The new compound is found in the course of studies of the phase diagram of the CsHSO{sub 4}–CsH{sub 2}PO{sub 4}–H{sub 2}O triple system. Data on the atomic crystal structure of single-crystalline and powder specimens, as well as on structural phase transitions, are obtained.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Magnetic remanence in Yb{sub 14−x}RE{sub x}MnSb{sub 11} (RE=Tb, Dy, Ho) single crystals

Single crystals of Yb{sub 14−x}RE{sub x}MnSb{sub 11} (x~0.1, 0.4; RE = Tb, Dy, Ho) have been prepared as a solid solution by Sn flux reactions of the elements. They crystallize in the Ca{sub 14}AlSb{sub 11} structure type in the I4{sub 1}/acd space group. The RE{sup 3+}preferentially substitutes on the Yb(1) site which is the smallest volume Yb containing polyhedron. In the case of Ho{sup 3+}, a small amount of Ho{sup 3+} also substitutes on the Yb(4) site. The ferromagnetic ordering temperature of Yb{sub 14}MnSb{sub 11} is reduced from 53 K to 41 K as x increases and dependent on the identity of the RE. This is attributed to the reduction in carriers and reduced screening of the Mn{sup 2+} local moment. The effective moments, μ{sub eff,} agree well with the calculated moments assuming the RE substitutes as a trivalent cation. The largest coercive field is observed for RE = Dy (1000 Oe). For the maximum x of Yb{sub 14−x}RE{sub x}MnSb{sub 11} there are enough carriers for the Ruderman-Kittel-Kasuya-Yosida (RKKY) mechanism of magnetic coupling via conduction electrons to still be valid in describing the ferromagnetic ordering. - Graphical abstract: Field dependent susceptibility loops revealed magnetic remanence in these materials, which has not been previously observed in Yb{sub 14}MnSb{sub 11} compounds. The coercive field increases with the strength of the paramagnetic moment for the substituting rare earth and the amount of the rare earth that is substituted. Display Omitted - Highlights: • Yb{sub 14−x}RE{sub x}MnSb{sub 11} (RE=Tb, Dy, & Ho) were synthesized with x~0.2 and x~0.4. • Tb, Dy, & Ho preferentially substitute on the Yb(1) site. • Samples with the largest x and largest RE moment have the largest coercive field. • There is a split between zero field cooled and field cooled susceptibility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗