NpSe2 : a Binary Chalcogenide Containing Modulated Selenide Chains and Ambiguous-Valent Metal.

A new binary compound, NpSe2, possesses metal-chalcogen and chalcogen-chalcogen interactions different from those reported for other metal dichalcogenides. Its structure is incommensurately modulated and features linear Se chains and valence-ambiguous Np cations.

In situ studies of a platform for metastable inorganic crystal growth and materials discovery.

Rapid shifts in the energy, technological, and environmental demands of materials science call for focused and efficient expansion of the library of functional inorganic compounds. To achieve the requisite efficiency, we need a materials discovery and optimization paradigm that can rapidly reveal all possible compounds for a given reaction and composition space. Here we provide such a paradigm via in situ X-ray diffraction measurements spanning solid, liquid flux, and recrystallization processes. We identify four new ternary sulfides from reactive salt fluxes in a matter of hours, simultaneously revealing routes for ex situ synthesis and crystal growth. Changing the flux chemistry, here accomplished by increasing sulfur content, permits comparison of the allowable crystalline building blocks in each reaction space. The speed and structural information inherent to this method of in situ synthesis provide an experimental complement to computational efforts to predict new compounds and uncover routes to targeted materials by design.

Understanding the role of aqueous solution speciation and its application to the directed syntheses of complex oxidic Zr chlorides and sulfates.

The lack of an in-depth understanding of solution-phase speciation and its relationship to solid-state phase formation is a grand challenge in synthesis science. It has severely limited the ability of inorganic chemists to predict or rationalize the formation of compounds from solutions. The need to investigate mechanisms that underlie self-assembly has motivated this study of aqueous Zr-sulfate chemistry as a model system, with the goal of understanding the structures of oligomeric clusters present in solution. We used high-energy X-ray scattering (HEXS) data to quantify Zr correlations in a series of solutions as a function of sulfate concentration. The pair distribution function (PDF) from the sulfate-free sample reveals that the average oligomeric Zr moiety is larger than the tetrameric building unit, [Zr4(OH)8(H2O)16](8+), generally understood to dominate its solution speciation. At sulfate concentrations greater than 1 m (molal), bidentate sulfate is observed, a coordination not seen in Zr(SO4)2·4H2O (2), which forms upon evaporation. Also seen in solution are correlations consistent with sulfate-bridged Zr dimers and the higher-order oligomers seen in 2. At intermediate sulfate concentrations there are correlations consistent with large Zr hydroxo-/oxo-bridged clusters. Crystals of [Zr18(OH)26O20(H2O)23.2(SO4)12.7]Cl0.6·nH2O (3) precipitate from these solutions. The Raman spectrum of 3 has a peak at 1017 cm(-1) that can be used as a signature for its presence in solution. Raman studies on deuterated solutions point to the important role of sulfate in the crystallization process. These solution results emphasize the presence of well-defined prenucleation correlations on length scales of <1 nm, often considered to be within the structurally amorphous regime.

Reinvestigation of Np2Se5: a clear divergence from Th2S5 and Th2Se5 in chalcogen-chalcogen and metal-chalcogen interactions.

Single crystals of Np2Se5 have been prepared through the reactions of Np and Se at 1223 K in an Sb2Se3 flux. The structure of Np2Se5, which has been characterized by single-crystal X-ray diffraction methods, crystallizes in the tetragonal space group P42/nmc. The crystallographic unit cell includes one unique Np and two Se positions. Se(1) atoms form one-dimensional infinite chains along the a and b axes with alternating intermediate Se-Se distances of 2.6489 (8) and 2.7999 (8) Å, whereas Se(2) is a discrete Se(2-) anion. Each Np is coordinated to 10 Se atoms and every NpSe10 polyhedron shares faces, edges, or vertices with 14 other identical metal polyhedra to form a complex three-dimensional structure. Np LIII-edge X-ray Absorption Near Edge Structure (XANES) measurements show a clear shift in edge position to higher energies for Np2Se5 compared to Np3Se5 (Np(3+)2Np(4+)Se(2-)5). Magnetic susceptibility measurements indicate that Np2Se5 undergoes a ferromagnetic-type ordering below 18(1) K. Above the transition temperature, Np2Se5 behaves as a paramagnet with an effective moment of 1.98(5) µB/Np, given by a best fit of susceptibilities to a modified Curie-Weiss law over the temperature range 50-320 K.

Preparation, stability, and structural characterization of plutonium(VII) in alkaline aqueous solution.

A freshly prepared solution of Pu(VI) in 2 M NaOH was oxidized to Pu(VII), via ozonolysis, while simultaneously collecting X-ray absorption spectra. Analyses of the XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) data, acquired throughout the in situ experiments, show a dioxo coordination environment for Pu(VI), PuO(2)(2+), typical for it and the hexavalent actinyl species of U and Np, and its evolution into a tetraoxo-coordination environment for Pu(VII), PuO(4)(-), like that known for Np(VII). The EXAFS data provide average Pu-O distances of 1.79(1) and 1.88(1) Å, respectively. The second coordination shells, also fit as O atoms, provide Pu-O distances of 2.29-2.32 Å that are independent of the Pu oxidation state. The coordination numbers for the distant O atoms in sums with those for the nearest O atoms are consistent with 6-O environments for both Pu(VI) and Pu(VII) ions in accordance with their previously proposed speciation as [Pu(VI)O(2)(OH)(4)](2-) and [Pu(VII)O(4)(OH)(2)](3-), respectively. This solution speciation accounts precisely for the Pu(VI) and Pu(VII) coordination environments reported in various solid state structures. The Pu(VII) tetraoxo-dihydroxo anion was found to have a half-life of 3.7 h. Its instability is attributed to spontaneous reduction to Pu(VI) and not to a measurable extent of disproportionation. We found no direct evidence for Pu(VIII) in the X-ray data and, furthermore, the stoichiometry of the oxidation of Cr(III) by Pu is consistent with that expected for a valence-pure Pu(VII) preparation by ozonation and, in turn, stoichiometrically equivalent to the established Np(VII)/Cr(III) redox reaction.

Intermediate-valence tautomerism in decamethylytterbocene complexes of methyl-substituted bipyridines.

Multiconfigurational, intermediate valent ground states are established in several methyl-substituted bipyridine complexes of bis(pentamethylcyclopentadienyl)ytterbium, Cp2*Yb (Me(x)-bipy). In contrast to Cp2*Yb(bipy) and other substituted-bipy complexes, the nature of both the ground state and the first excited state are altered by changing the position of the methyl or dimethyl substitutions on the bipyridine rings. In particular, certain substitutions result in multiconfigurational, intermediate valent open-shell singlet states in both the ground state and the first excited state. These conclusions are reached after consideration of single-crystal X-ray diffraction (XRD), the temperature dependence of X-ray absorption near-edge structure (XANES), extended X-ray absorption fine-structure (EXAFS), and magnetic susceptibility data, and are supported by CASSCF-MP2 calculations. These results place the various Cp2*Yb(bipy) complexes in a new tautomeric class, that is, intermediate-valence tautomers.

Decamethylytterbocene complexes of bipyridines and diazabutadienes: multiconfigurational ground states and open-shell singlet formation.

Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C(5)Me(5))(2)Yb, abbreviated as Cp*(2)Yb. Data used to support this claim include ytterbium valence measurements using Yb L(III)-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground-state wave function that has both an open-shell singlet f(13)(pi*)(1), where pi* is the lowest unoccupied molecular orbital of the bipyridine or diazabutadiene ligands, and a closed-shell singlet f(14) component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices.

(2,2-Bipyrid-yl)bis-(η-penta-methyl-cyclo-penta-dien-yl)strontium(II).

In the title compound, [Sr(C(10)H(15))(2)(C(10)H(8)N(2))], the Sr-N distances are 2.624 (3) and 2.676 (3) Å, the Sr⋯Cp ring centroid distances are 2.571 and 2.561 Šand the N-C-C-N torsion angle in the bipyridine ligand is -2.2 (4)°. Inter-estingly, the bipyridine ligand is tilted. The angle between the plane defined by the Sr atom and the two bipyridyl N atoms and the plane defined by the 12 atoms of the bipyridine ligand is 10.7 (1)°.