Hybrid uranium-transition-metal oxide cage clusters.

Transition-metal based polyoxometalate clusters have been known for decades, whereas those built from uranyl peroxide polyhedra have more recently emerged as a family of complex clusters. Here we report the synthesis and structures of six nanoscale uranyl peroxide cage clusters that contain either tungstate or molybdate polyhedra as part of the cage, as well as phosphate tetrahedra. These transition-metal-uranium hybrid clusters exhibit unique polyhedral connectivities and topologies that include 6-, 7-, 8-, 10-, and 12-membered rings of uranyl polyhedra and uranyl ions coordinated by bidentate peroxide in both trans and cis configurations.

Incorporation of Cu(2+) ions into nanotubular uranyl diphosphonates.

Three new multidimensional polymetallic uranyl diphosphonates were crystallized under mild hydrothermal conditions: [Cu(H2O)]2{(UO2)4F2[(PO3C6H4)(C6H4PO3H)3]2(bipym)}·6H2O (1), [Cu(H2O)]2{(UO2)4[(C6H4PO3)(C6H4PO3H)]4(bipym)} (2), and Cu{(UO2)(C6H4PO3)2(bipym)}·H2O (3). Compound 1 consists of UO6F pentagonal bipyramids connected by diphosphonate moieties into a tubular channel. The Cu(2+) cations are stabilized between the nanotubular subunits by 2,2'-bipyrimidine (bipym).

A6U3Sb2P8S32 (A = Rb, Cs): quinary uranium(IV) thiophosphates containing the [Sb(PS4)3](6-) anion.

The reaction of A2S3/U/P2S5/S at 500 °C affords the quinary U(IV) thiophosphates A6U3Sb2P8S32 (A = Rb, Cs). These compounds contain {U3(PS4)2[Sb(PS4)3]2}(6-) layers separated by alkali metal cations. The layers are composed of trimeric uranium units connected to each other by the thiophosphato-antimonite anion, [Sb(PS4)3](6-).

Thermochromism, the Alexandrite effect, and dynamic Jahn-Teller distortions in Ho2Cu(TeO3)2(SO4)2.

A 3d-4f heterobimetallic material with mixed anions, Ho2Cu(TeO3)2(SO4)2, has been prepared under hydrothermal conditions. Ho2Cu(TeO3)2(SO4)2 exhibits both thermochromism and the Alexandrite effect. Variable temperature single crystal X-ray diffraction and UV-vis-NIR spectroscopy reveal that changes in the Cu(II) coordination geometry result in negative thermal expansion of axial Cu-O bonds that plays a role in the thermochromic transition of Ho2Cu(TeO3)2(SO4)2.

Synthesis, structure, and spectroscopy of two ternary uranium(IV) thiophosphates: UP2S9 and UP2S7 containing P2S9(2-) and P2S7(2-) ligands.

The two ternary uranium thiophosphate compounds were isolated from polychalcogenide flux reactions. UP2S9 crystallizes in the tetragonal space group P42/mcm with two formula units per unit cell, where a = 7.762(1) and c = 9.

From yellow to black: dramatic changes between cerium(IV) and plutonium(IV) molybdates.

Hydrothermal reactions of CeCl(3) and PuCl(3) with MoO(3) and Cs(2)CO(3) yield surprisingly different results. Ce(3)Mo(6)O(24)(H(2)O)(4) crystallizes as bright yellow plates (space group C2/c, a = 12.7337(7) Å, b = 22.

Synthesis, structure, magnetism, and optical properties of Cs2Cu3DyTe4.

CsCu(3)DyTe(4) was prepared by reacting copper, dysprosium, and tellurium with cesium azide at 850 °C in a fused silica ampule. This new telluride crystallizes in the monoclinic space group C2/m with lattice dimensions of a = 16.462(4) Å, b = 4.