89 research outputs found
Conversion of lanthanide glutarate chlorides with interstitial THF into lanthanide glutarates with unprecedented topologies
Using slow diffusion methods at room temperature (RT), we obtained four isomorphous lanthanide glutarate chlorides, accommodating interstitial THF and water molecules, [Ln2(Glut)2Cl2(H2O)8]•2H2O•THF (1 - 4), with Ln = La (1), Ce (2), Pr (3), Nd (4). They assemble as 3-dimensional (3D) lanthanide (Ln) coordination polymers with LnO10 coordination polyhedra. Their topology was elucidated to be a 4-coordinated sql net. 1 – 4 slowly dissolve in water liberating the entrapped THF molecules and reassemble as regular Ln-glutarate hydrates when the solution is deprived of THF and water by slow evaporation. The new products crystallize as [Ln2(Glut)3(H2O)3]•5H2O (5 - 7), with Ln = La (5), Ce (6), Pr (7), and [Nd2(Glut)3(H2O)2]•3.5H2O (8). 5 – 7 are isomorphous and crystallize as 3D-networks with two crystallographically independent LnO10 and LnO9 coordination spheres that assemble into Ln2O18 and Ln2O16 polyhedra via edge sharing. Their topology has not previously been observed and was found to be a 3,4,4,5,6-coordinated 3,4,4,5,6T61 net. The known compound 8 crystallizes also as a 3D-network and is isomorphous to other previously described lanthanide glutarate hydrates. 8 has a 3,4,5-coordinated 3,4,5T202 net topology, which has not been determined before
A Compact Dispersive Refocusing Rowland Circle X-ray Emission Spectrometer for Laboratory, Synchrotron, and XFEL Applications
X-ray emission spectroscopy is emerging as an important complement to x-ray
absorption fine structure spectroscopy, providing a characterization of the
occupied electronic density of states local to the species of interest. Here,
we present details of the design and performance of a compact x-ray emission
spectrometer that uses a dispersive refocusing Rowland (DRR) circle geometry to
achieve excellent performance for the 2 - 2.5 keV energy range. The DRR
approach allows high energy resolution even for unfocused x-ray sources. This
property enables high count rates in laboratory studies, comparable to those of
insertion-device beamlines at third-generation synchrotrons, despite use of
only a low-powered, conventional x-ray tube. The spectrometer, whose overall
scale is set by use of a 10-cm diameter Rowland circle and a new small-pixel
CMOS x-ray camera, is easily portable to synchrotron or x-ray free electron
beamlines. Photometrics from measurements at the Advanced Light Source show
somewhat higher overall instrumental efficiency than prior systems based on
less tightly curved analyzer optics. In addition, the compact size of this
instrument lends itself to future multiplexing to gain large factors in net
collection efficiency, or its implementation in controlled gas gloveboxes
either in the lab or in an endstation.Comment: Submitted, Review of Scientific Instrument
Synthesis and Characterization of A Tetrathiafulvalene-Salphen Actinide Complex
A new tetrathiafulvalene-salphen uranyl complex has been prepared. The system was designed to study the electronic coupling between actinides and a redox active ligand framework. Theoretical and experimental methods - including DFT calculations, single crystal X-ray analysis, cyclic voltammetry, NMR and IR spectroscopies - were used to characterize this new uranyl complex.Office of Basic Energy Sciences, U. S. Department of Energy (DOE) DE-FG02-01ER15186Ministry of Education, Science and TechnologyHeavy Element Chemistry Program by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of EnergyGlenn T. Seaborg InstituteNational Nuclear Security Administration of U.S. Department of Energy DE-AC52-06NA25396Chemistr
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Energy-Degeneracy-Driven Covalency in Actinide Bonding
Evaluating the nature of chemical bonding for actinide elements represents one of the most important and long-standing problems in actinide science. We directly address this challenge and contribute a Cl K-edge X-ray absorption spectroscopy and relativistic density functional theory study that quantitatively evaluates An–Cl covalency in AnCl62– (AnIV = Th, U, Np, Pu). The results showed significant mixing between Cl 3p- and AnIV 5f- and 6d-orbitals (t1u*/t2u* and t2g*/eg*), with the 6d-orbitals showing more pronounced covalent bonding than the 5f-orbitals. Moving from Th to U, Np, and Pu markedly changed the amount of M–Cl orbital mixing, such that AnIV 6d- and Cl 3p-mixing decreased and metal 5f- and Cl 3p-orbital mixing increased across this series
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Crystallographic characterization of (C5H4SiMe3)3U(BH4).
New syntheses have been developed for the synthesis of (borohydrido-κ3 H)tris-[η5-(tri-methyl-sil-yl)cyclo-penta-dien-yl]uranium(IV), [U(BH4)(C8H13Si)3] or Cp'3U(BH4) (Cp' = C5H4SiMe3) and its structure has been determined by single-crystal X-ray crystallography. This compound crystallized in the space group P and the structure features three η 5-coordinated Cp' rings and a κ 3-coordinated (BH4)- ligand
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