Effects of large halides on the structures of lanthanide(III) and plutonium(III) borates

Reactions of LnBr(3) or LnOI with molten boric acid result in formation of Ln[B(5)O(8)(OH)(H(2)O)(2)Br] (Ln = La-Pr), Nd(4)[B(18)O(25)(OH)(13)Br(3)], or Ln[B(5)O(8)(OH)(H(2)O)(2)I] (Ln = La-Nd). Reaction of PuOI with molten boric acid yields Pu[B(7)O(11)(OH)(H(2)O)(2)I]. The Ln(III) and Pu(III) centers in these compounds are found as nine-coordinate hula-hoop or 10-coordinate capped triangular cupola geometries where there are six approximately coplanar oxygen donors provided by triangular holes in the polyborate sheets. The borate sheets are connected into three-dimensional networks by additional BO(3) triangles and/or BO(4) tetrahedra that are roughly perpendicular to the layers. The room-temperature absorption spectrum of single crystals of Pu[B(7)O(11)(OH)(H(2)O)(2)I] shows characteristic f-f transitions for Pu(III) that are essentially indistinguishable from Pu(III) in other compounds with alternative ligands and different coordination environments.     

An approximate treatment of scattering based on the delta boundary operator

The development of a scheme to treat two-dimensional electromagneticscattering by electrically large, perfectly conducting bodiesis described. It incorporates the effects of surface curvatureand non-local phenomena and has the potential to provide thebasis for a general technique yielding more accurate predictionsthan the widely used physical optics method.     

General route to three-dimensional framework uranyl transition metal phosphates with atypical structural motifs: the case examples of Cs2{(UO2)4[Co(H2O)2]2(HPO4)(PO4)4} and Cs3+x[(UO2)3CuH4-x(PO4)5].H2O

The reaction of UO2(NO3)2.6H2O with Co or Cu metal, phosphoric acid, and CsCl under mild hydrothermal conditions results in the formation of Cs2{(UO2)4[Co(H2O)2(HPO4)(PO4)4} (1) or Cs(3+x)[(UO2)3CuH(4-x)(PO4)5].H2O (2). The structure of 1 contains uranium atoms in pentagonal bipyramidal and hexagonal bipyramidal environments. The interaction of the uranyl cations and phosphate anions creates layers in the [ab] plane. The uranyl phosphate layers are joined together by octahedral Co centers wherein the Co is bound by phosphate and two cis water molecules. In addition, the Co ions are also ligated by a uranyl oxo atom. The presence of these octahedral building units stitches the structure together into a three-dimensional framework where void spaces are filled by Cs+ cations. The structure of 2 contains uranium centers in UO6 tetragonal bipyramidal and UO7 pentagonal bipyramidal geometries. The uranyl moieties are bridged by phosphate anions into sinusoidal sheets that extend into the [bc] plane and are linked into a three-dimensional structure by Cu(II). The Cu centers reside in square planar environments. Charge balance is maintained by Cs+ cations. Both the overall structures and the uranyl phosphate layers in 1 and 2 are novel.     

Structural polarity induced by cooperative hydrogen bonding and lone-pair alignment in the molecular uranyl iodate Na2[UO2(IO3)4(H2O)

Na2[UO2(IO3)4(H2O)] has been synthesized under mild hydrothermal conditions. Its structure consists of Na+ cations and [UO2(IO3)4(H2O)](2-) anions. The [UO2(IO3)4(H2O)](2-) anions are formed from the coordination of a nearly linear uranyl, UO2(2+), cation by four monodentate IO(3-) anions and a coordinating water molecule to yield a pentagonal bipyramidal environment around the uranium center. The water molecules form intermolecular hydrogen bonds with the terminal oxo atoms of neighboring [UO2(IO3)4(H2O)](2-) anions to yield one-dimensional chains that extend down the b axis. There are two crystallographically unique iodate anions in the structure of Na2[UO2(IO3)4(H2O)]. One of these anions is aligned so that the lone-pair of electrons is also directed along the b axis. The overall structure is therefore polar, owing to the cooperative alignment of both the hydrogen bonds and the lone-pair of electrons on iodate. The polarity of the monoclinic space group C2 (a = 11.3810(12) A, b = 8.0547(8) A, c = 7.6515(8) A, beta = 90.102(2) degrees , Z = 2, T = 193 K) found for this compound is consistent with the structure. Second-harmonic generation of 532 nm light from a 1064 nm laser source yields a response of approximately 16x alpha-SiO2.     

Unusual case of a polar copper(II) uranyl phosphonate that fluoresces

A polar Cu(II) uranyl diphosphonate, Cu(H₂O)₄(UO₂)₃(H₂O)₂[CH₂(PO₃)₂]₂·5H₂O, has been prepared under mild hydrothermal conditions. This compound has direct linkages between the oxo atoms of the uranyl moieties and the Cu(II) centers. Despite the presence of Cu(II) in the structure, vibronically-coupled emission is still observed, most likely because there are two crystallographically unique uranyl moieties, only one of which bonds to Cu(II).     

Structural characterization of the first hydrothermally synthesized plutonium compound,PuO2(IO3)2 x H2O

Single crystals of PuO2(IO3)2 x H2O were synthesized under hydrothermal conditions (180 degrees C) representing the first structurally characterized transuranium iodate.     

Syntheses, structure, magnetism, and optical properties of the interlanthanide sulfides δ-Ln2−xLuxS3 (Ln=Ce, Pr, Nd)

δ-Ln_2−xLu_xS₃ (Ln=Ce, Pr, Nd; x=0.67-0.71) compounds have been synthesized through the reaction of elemental rare-earth metals and S using a Sb₂S₃ flux at 1000 °C. These compounds are isotypic with CeTmS₃, which has a complex three-dimensional structure. It includes four larger Ln³⁺ sites in eight- and nine-coordinate environments, two disordered seven-coordinate Ln³⁺/Lu³⁺ positions, and two six-coordinate Lu³⁺ ions. The structure is constructed from one-dimensional chains of LnS_n (n=6-9) polyhedra that extend along the b-axis. These polyhedra share faces or edges with two neighbors within the chains, while in the [ac] plane they share edges and corners with other chains. Least square refinements gave rise to the formulas of δ-Ce_1.30Lu_0.70S₃, δ-Pr_1.29Lu_0.71S₃ and δ-Nd_1.33Lu_0.67S₃, which are consistent with the EDX analysis and magnetic susceptibility data. δ-Ln_2−xLu_xS₃ (Ln=Ce, Pr, Nd; x=0.67-0.71) show no evidence of magnetic ordering down to 5 K. Optical properties measurements show that the band gaps for δ-Ce_1.30Lu_0.70S₃, δ-Pr_1.29Lu_0.71S₃, and δ-Nd_1.33Lu_0.67S₃ are 1.25, 1.38, and 1.50 eV, respectively. Crystallographic data: δ-Ce_1.30Lu_0.70S₃, monoclinic, space group P2₁/m, a=11.0186(7), b=3.9796(3), c=21.6562(15) Å, β=101.6860(10), V=929.93(11), Z=8; δ-Pr_1.29Lu_0.71S₃, monoclinic, space group P2₁/m, a=10.9623(10), b=3.9497(4), c=21.5165(19) Å, β=101.579(2), V=912.66(15), Z=8; δ-Nd_1.33Lu_0.67S₃, monoclinic, space group P2₁/m, a=10.9553(7), b=3.9419(3), c=21.4920(15) Å, β=101.5080(10), V=909.47(11), Z=8.     

Hydrothermal synthesis, structure, and magnetic properties of the mixed-valent Np(IV)/Np(V) Selenite Np(NpO2)2(SeO3)3

The reaction of NpO(2) with SeO(2) in the presence of CsCl at 180 degrees C results in the formation of Np(NpO(2))(2)(SeO(3))(3) (1). The structure of 1 consists of three crystallographically unique Np centers with three different coordination environments in two different oxidation states. Np(1) is found in a neptunyl(V), O[double bond]Np[double bond]O(+), unit that is further ligated in the equatorial plane by three chelating SeO(3)(2-) anions to create a hexagonal bipyramidal NpO(8) unit. A second neptunyl(V) cation also occurs for Np(2); it is bound by four bridging selenite anions and by the oxo atom from the Np(1) neptunyl cation to form a pentagonal bipyramidal, NpO(7), unit. The third neptunium center, Np(3), which contains Np(IV), is found in a distorted NpO(8) dodecahedron. Np(3) is bound by five bridging selenite anions and by three neptunyl units via cation-cation interactions. The NpO(7) pentagonal bipyramids and NpO(8) hexagonal bipyramids share both corners and edges. Both of these polyhedra share corners via cation-cation interactions with the NpO(8) dodecahedra creating a three-dimensional structure with small channels that house the stereochemically active lone pair of electrons on the selenite anions. Magnetic susceptibility data follow Curie-Weiss behavior over the entire temperature range measured (5 < or = T < or = 320 K). The effective moment, mu(eff) = 2.28 mu(B), which represents an average over the three crystallographically inequivalent Np atoms, is within the expected range of values. There is no evidence of long-range ordering of the Np moments at temperatures down to 5 K, consistent with the negligible Weiss constant determined from fitting the susceptibility data. Crystallographic data: 1, orthorhombic, space group Pbca, a = 10.6216(5), b = 11.9695(6), and c = 17.8084(8) A and Z = 8 (T = 193 K).