Intercalative Ion Exchange of Polyamine Transition Metal Complexes into Hydrogen Uranyl Phosphate

Abstract

A series of derivatives of hydrogen uranyl phosphate (HUP) was prepared by displacing the butylammonium ions of butylammonium uranyl phosphate with the transition metal complexes Cu(en)(2)(2+), Cu(pn)(2)(2+), Cu(trien)(2+), Cu(14-ane)(2+), Cu(15-ane)(2+), Ni(trien)(2+), Ni(14-ane)(2+), and Ni(diene)(2+). X-ray powder patterns proved that the original tetragonal structure of the UP layers remained intact in all derivatives. The extent of the ion exchange and the interlamellar distances were found to depend mainly on the size and on the shape of a particular coordinating ligand. Electronic absorption spectra indicated that the intercalated complexes had four-coordinate square-planar geometry inside the UP lattice. Extents of hydration of the intercalates varied significantly, and they depended mostly on the shapes of the coordinating ligands and on their abilities to regularly pack between the UP layers. Results of the above-mentioned characteristics allow one to divide these transition metal complexes into two groups which differ from each other in their abilities to efficiently fill up the space between the UP layers. The steady-state luminescence spectra of intercalates showed a very weak uranyl emission which was partly due to quenching by the Cu(2+) and Ni(2+) guest complexes and partly to self-absorption.

Crystal chemistry and ion-exchange properties of the layered uranyl iodate K[UO2(IO3)3]

“…In addition, certain uranyl compounds such as hydrogen uranyl phosphate (HUP) [40][41][42][43] and Cs 4 [(UO 2 ) 2 (V 2 O 7 )O 2 ] [44] have been shown to exhibit high cationic conductivities. In order to evaluate the potential for ion-exchange reactions of alkali metal cations with 1, samples were equilibrated with 0.01 M solutions of NaCl/NaOH, KCl/KOH, or CsCl/CsOH.…”

Barium uranyl diphosphonates

“…Based on these new structures, the topological relations can be discerned [5] and used as a basis for materials design yielding solids with specific properties: e.g. selective ion-exchange [6][7][8][9][10][11][12], mixed-valency [13,14], ionic conductivity [15][16][17][18][19][20], enhanced fluorescence [21][22][23], magnetic ordering [11,24], non-linear optical properties [12,25], and differential gas absorption [26,27].…”

The First Fully Fluorinated Organically Templated Materials: Synthesis, Structures, and Physical Properties of [H3N(CH2)3NH3]U2F10·2H2O, [H3N(CH2)4NH3]U2F10·3H2O, [H3N(CH2)6NH3]U2F10·2H2O, and [HN(CH2CH2NH3)3]U5F24Francis1, Halasyamani2, O’Hare3 1998Chem. Mater.633442View full textAdd to dashboardCite

“…Clearfield and co-workers have demonstrated that in the synthesis of uranyl phosphonates, the presence of sterically demanding organic groups on the phosphonate ligands leads to the formation of novel structure types, including porous structures. − Second, these materials may be envisioned to exhibit useful catalytic, ion-exchange, and intercalation properties. For example, hydrogen uranyl phosphate (HUP) is a fast hydrogen ion conductor and a versatile ion-exchange reagent, − and Hutchings et al recently demonstrated that uranium oxide-based materials are effective oxidation catalysts for the destruction of a range of hydrocarbon- and chlorine-containing industrial pollutants . Finally, the existence of a number of stable oxidation states of actinides, such as uranium, offers the possibility of synthesising materials with useful optical and magnetic properties.…”