[Ag₂M(Te₂O₅)₂]SO₄ (M = Ce^IV or Th^IV): A New Purely Inorganic d/f-Heterometallic Cationic Material

Two new isotypic d/f-heterometallic purely inorganic cationic materials, [Ag₂M­(Te₂O₅)₂]­SO₄ (M = Ce^IV or Th^IV), were synthesized using the metal oxides (MO₂ and TeO₂), silver nitrate, and sulfuric acid under mild hydrothermal conditions. The prepared materials were characterized via single-crystal X-ray diffraction, which revealed that the materials possess a 3D framework of corner-sharing Te₂O₅^2– units. The tellurite framework creates four unique pores, three of which are occupied by the M^IV and Ag^I metal centers. The tellurite network, metal coordination, and total charge yield a cationic framework, which is charge-balanced by electrostatically bound sulfate anions residing in the largest of the four framework pores. These materials also possess Ag^I in a ligand-imposed linear geometry

Incorporation of Neptunium(VI) into a Uranyl Selenite

The incorporation of neptunium­(VI) into the layered uranyl selenite Cs­[(UO₂)­(HSeO₃)­(SeO₃)] has yielded the highest level of neptunium uptake in a uranyl compound to date with an average of 12(±3)% substitution of Np^VI for U^VI. Furthermore, this is the first case in nearly 2 decades of dedicated incorporation studies in which the oxidation state of neptunium has been determined spectroscopically in a doped uranyl compound and also the first time in which neptunium incorporation has resulted in a structural transformation

Ionothermal and Hydrothermal Flux Syntheses of Five New Uranyl Phosphonates

Four new uranyl phosphonate compounds have been synthesized via ionothermal flux in the ionic liquids 1-butyl-3-methylimidazolium chloride ([Bmim]­[Cl]) and 1-ethyl-3-methylimidazolium bromide ([Emim]­[Br]). [C₈H₁₅N₂]­[UO₂(C₆H₅PO₃H)­(C₆H₅PO₃)] (<b>[Bmim]­[UPhPO]</b>), [C₈H₁₅N₂]₂[(UO₂)₄(C₆H₅PO₃)₃Cl₄] (<b>[Bmim]­[UPhPOCl]</b>), [C₈H₁₅N₂]­[UO₂(HO₃P­(CH₂)₃PO₃)] (<b>α-[Bmim]­[UC</b>_<b>3</b><b>DPO]</b>), and [C₆H₁₁N₂]₂[(UO₂)₂(<i>p</i>-C₆H₄(PO₃H)₂)₃]·2H₂O (<b>[Emim]­[UPhDPO]</b>) form one-dimensional chains, two-dimensional sheets, or three-dimensional frameworks. For comparison, analogous reactions were carried out hydrothermally, which lead to one new framework structure, [C₈H₁₅N₂]₂[(UO₂)₅(HO₃P­(CH₂)₃PO₃)₄] (<b>β-[Bmim]­[UC</b>_<b>3</b><b>DPO]</b>), and one previously characterized tubular uranyl phosphonate. It was found that the structure is equally dictated by the choice of flux method, the choice of ligand, and the choice of ionic liquid

Synthesis and Spectroscopy of New Plutonium(III) and -(IV) Molybdates: Comparisons of Electronic Characteristics

Synthesis of a plutonium­(III) molybdate bromide, PuMoO₄Br­(H₂O), has been accomplished using hydrothermal techniques in an inert-atmosphere glovebox. The compound is green in color, which is in stark contrast to the typical blue color of plutonium­(III) complexes. The unusual color arises from the broad charge transfer (CT) spanning from approximately 300 to 500 nm in the UV–vis–near-IR spectra. Repeating the synthesis with an increase in the reaction temperature results in the formation of a plutonium­(IV) molybdate, Pu₃Mo₆O₂₄(H₂O)₂, which also has a broad CT band and red-shifted f–f transitions. Performing an analogous reaction with neodymium produced a completely different product, [Nd­(H₂O)₃]­[NdMo₁₂O₄₂]·2H₂O, which is built of Silverton-type polyoxometallate clusters

Ionothermal and Hydrothermal Flux Syntheses of Five New Uranyl Phosphonates

Four new uranyl phosphonate compounds have been synthesized via ionothermal flux in the ionic liquids 1-butyl-3-methylimidazolium chloride ([Bmim]­[Cl]) and 1-ethyl-3-methylimidazolium bromide ([Emim]­[Br]). [C₈H₁₅N₂]­[UO₂(C₆H₅PO₃H)­(C₆H₅PO₃)] (<b>[Bmim]­[UPhPO]</b>), [C₈H₁₅N₂]₂[(UO₂)₄(C₆H₅PO₃)₃Cl₄] (<b>[Bmim]­[UPhPOCl]</b>), [C₈H₁₅N₂]­[UO₂(HO₃P­(CH₂)₃PO₃)] (<b>α-[Bmim]­[UC</b>_<b>3</b><b>DPO]</b>), and [C₆H₁₁N₂]₂[(UO₂)₂(<i>p</i>-C₆H₄(PO₃H)₂)₃]·2H₂O (<b>[Emim]­[UPhDPO]</b>) form one-dimensional chains, two-dimensional sheets, or three-dimensional frameworks. For comparison, analogous reactions were carried out hydrothermally, which lead to one new framework structure, [C₈H₁₅N₂]₂[(UO₂)₅(HO₃P­(CH₂)₃PO₃)₄] (<b>β-[Bmim]­[UC</b>_<b>3</b><b>DPO]</b>), and one previously characterized tubular uranyl phosphonate. It was found that the structure is equally dictated by the choice of flux method, the choice of ligand, and the choice of ionic liquid

Synthesis and Spectroscopy of New Plutonium(III) and -(IV) Molybdates: Comparisons of Electronic Characteristics

Synthesis of a plutonium­(III) molybdate bromide, PuMoO₄Br­(H₂O), has been accomplished using hydrothermal techniques in an inert-atmosphere glovebox. The compound is green in color, which is in stark contrast to the typical blue color of plutonium­(III) complexes. The unusual color arises from the broad charge transfer (CT) spanning from approximately 300 to 500 nm in the UV–vis–near-IR spectra. Repeating the synthesis with an increase in the reaction temperature results in the formation of a plutonium­(IV) molybdate, Pu₃Mo₆O₂₄(H₂O)₂, which also has a broad CT band and red-shifted f–f transitions. Performing an analogous reaction with neodymium produced a completely different product, [Nd­(H₂O)₃]­[NdMo₁₂O₄₂]·2H₂O, which is built of Silverton-type polyoxometallate clusters

Unusual Coordination for Plutonium(IV), Cerium(IV), and Zirconium(IV) in the Cationic Layered Materials [M₂Te₄O₁₁]X₂ (M = Pu, Ce, Zr; X = Cl, Br)

Four isotypic cationic layered materials, [Pu₂Te₄O₁₁]­Cl₂, [Ce₂Te₄O₁₁]­Cl₂, [Zr₂Te₄O₁₁]­Cl₂, and [Zr₂Te₄O₁₁]­Br₂, have been prepared under hydrothermal conditions. Single crystal diffraction studies reveal that these materials possess cationic Pu/Ce/Zr tellurite layers with halides as interlamellar charge-balancing anions. The Pu^IV, Ce^IV, and Zr^IV centers of the cationic layers exhibit a quite rare pentagonal bipyramid coordination environment

Syntheses, Structures, and Spectroscopic Properties of Plutonium and Americium Phosphites and the Redetermination of the Ionic Radii of Pu(III) and Am(III)

A series of isotypic rare earth phosphites (RE = Ce­(III), Pr­(III), Nd­(III), Pu­(III), or Am­(III)) with the general formulas RE₂(HPO₃)₃(H₂O) along with a Pu­(IV) phosphite, Pu­[(HPO₃)₂(H₂O)₂], have been prepared hydrothermally via reactions of RECl₃ with phosphorous acid. The structure of RE₂(HPO₃)₃(H₂O) features a face-sharing interaction of eight- and nine-coordinate rare earth polyhedra. By use of the crystallographic data from the isotypic series along with data from previously reported isotypic series, the ionic radii for higher coordinate Pu­(III) and Am­(III) were calculated. The ^VIIIPu­(III) radius was calculated as 1.112 ± 0.004 Å, and the ^IXPu­(III) radius was calculated to be 1.165 ± 0.002 Å. The ^VIIIAm­(III) radius was calculated as 1.108 ± 0.004 Å, and the ^IXAm­(III) radius was calculated as 1.162 ± 0.002 Å

Unusual Coordination for Plutonium(IV), Cerium(IV), and Zirconium(IV) in the Cationic Layered Materials [M₂Te₄O₁₁]X₂ (M = Pu, Ce, Zr; X = Cl, Br)

Four isotypic cationic layered materials, [Pu₂Te₄O₁₁]­Cl₂, [Ce₂Te₄O₁₁]­Cl₂, [Zr₂Te₄O₁₁]­Cl₂, and [Zr₂Te₄O₁₁]­Br₂, have been prepared under hydrothermal conditions. Single crystal diffraction studies reveal that these materials possess cationic Pu/Ce/Zr tellurite layers with halides as interlamellar charge-balancing anions. The Pu^IV, Ce^IV, and Zr^IV centers of the cationic layers exhibit a quite rare pentagonal bipyramid coordination environment

Syntheses, Structures, and Spectroscopic Properties of Plutonium and Americium Phosphites and the Redetermination of the Ionic Radii of Pu(III) and Am(III)

A series of isotypic rare earth phosphites (RE = Ce­(III), Pr­(III), Nd­(III), Pu­(III), or Am­(III)) with the general formulas RE₂(HPO₃)₃(H₂O) along with a Pu­(IV) phosphite, Pu­[(HPO₃)₂(H₂O)₂], have been prepared hydrothermally via reactions of RECl₃ with phosphorous acid. The structure of RE₂(HPO₃)₃(H₂O) features a face-sharing interaction of eight- and nine-coordinate rare earth polyhedra. By use of the crystallographic data from the isotypic series along with data from previously reported isotypic series, the ionic radii for higher coordinate Pu­(III) and Am­(III) were calculated. The ^VIIIPu­(III) radius was calculated as 1.112 ± 0.004 Å, and the ^IXPu­(III) radius was calculated to be 1.165 ± 0.002 Å. The ^VIIIAm­(III) radius was calculated as 1.108 ± 0.004 Å, and the ^IXAm­(III) radius was calculated as 1.162 ± 0.002 Å