Use of Bifunctional Phosphonates for the Preparation of Heterobimetallic 5f−3d Systems

Abstract

The hydrothermal reaction of phosphonoacetic acid (H2PO3CH2C(O)OH, PAA) with UO3 and Cu(C2H3O2)2 .H2O results in the formation of the crystalline heterobimetallic uranium(VI)/copper(II) phosphonates UO2Cu(PO3CH2CO2)(OH)(H2O)2 ( UCuPAA-1), (UO2) 2Cu(PO3CH2CO2)2(H2O)3 (UCuPAA-2), and [H3O][(UO2) 2Cu2(PO3CH2CO2)3(H2O)2 ( UCuPAA-3). The addition of sodium hydroxide to the aforementioned reactions results in the formation of Na[UO2(PO3CH2CO2)].2H2O (NaUPAA-1). These compounds display 1D (UCuPAA-1), 2D (UCuPAA-2, NaUPAA-1), and 3D (UCuPAA-3) architectures wherein the phosphonate portion of the ligand primarily coordinates the uranium(VI) centers; whereas the carboxylate moiety preferentially, but not exclusively, binds to the copper(II) ions. Fluorescence measurements on all four compounds demonstrate that the presence of copper(II) mostly quenches the emission from the uranyl moieties.

Crown Ethers and Their Alkali Metal Ion Complexes as Assembler Groups in Uranyl–Organic Coordination Polymers with cis-1,3-, cis-1,2-, and trans-1,2-Cyclohexanedicarboxylates

“…Atoms U1 and U3 are both chelated between the two carboxylate groups of one c-1,2-chdc 2-ligand, bound to one more respectively, and Na1 is also coordinated to the uranyl oxo atom O1 with a bond length of 2.502 (11) Å, a value within the usual range for these rather common bonds. 21,[48][49][50][51][52][53][54] The packing displays an alternation of uranyl-containing polymeric sheets and layers occupied by the [Na(15C5)] + appendages. In the absence of water molecules, interactions between the sheets appear to involve largely CH···O contacts of the polyether units.…”

Synthesis and Characterization of 1‐, 2‐, and 3‐Dimensional Bimetallic UO22+/Zn2+ Phosphonoacetates

“…[1][2][3] In spite of this relevance to separations and nuclear fuel stewardship, our knowledge of the structural chemistry of actinide phosphonates has largely been limited to those uranyl phenylphosphonates reported by Clearfield et al, [4][5][6][7][8][9][10][11][12] as well as a handful of other compounds. [13][14][15][16][17][18] More recently, in an effort to probe the structural chemistry of uranyl phosphonate compounds and extend the known catalog of these materials beyond monophosphonates, the interaction of UO 2 2+ with polyphosphonate [19][20][21][22][23][24] and carboxyphosphonate ligands [25][26][27] has been explored. These ligands are attractive candidates for materials synthesis due to the range of metal-to-ligand binding modes and the potential for novel structural topologies.…”

“…[35] Whereas a number of UO 2 2+ -carboxylate structures have been synthesized, [36][37][38][39][40][41][42][43][44][45][46][47][48][49] far fewer examples of solid-state UO 2 2+ -carboxyphosphonate architectures have been reported. [25][26][27] The interaction of UO 2 2+ with bacterial cell-wall components, such as lipopolysaccharide, that contain high concentrations of phosphoryl and carboxyl groups has been explored in solution. [29] In these studies, the uranyl cation displayed coordination preference for the harder -PO 3 over the -CO 2 functionality.…”

“…[25][26][27] In fact, in the solid state, the propensity of the uranyl cation to bind preferentially to the phosphonate moieties over the carboxylate units was exploited by Albrecht-Schmitt et al to construct a series of heterometallic UO 2 2+ /Cu 2+ /PPA compounds. [27] Beyond the bimetallic UO 2 2+ /Cu 2+ materials reported, however, the incorporation of other transition metal cations into UO 2 2+ /PPA systems has not yet been explored. As such, we investigated reactions of uranium(VI) and triethyl phosphonoacetate in the presence of zinc under hydrothermal conditions.…”

Molecular Copper(II) Complexes Derived from Phosphonoacetic Acid: Crystal Structures and Magnetic Behavior

“…Centering on the research of phosphonoacetic acid (Scheme 1), there exists a large number of structurally solved published compounds with only one type of metallic cation [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] and several published compounds with two different metallic cations, mainly, uranyl-M 2+ (M = Zn, Cu, or Mn). [21][22][23][24][25][26][27] The structurally solved published compounds are usually 2D and 3D compounds. Only a few of the reported compounds are molecular mononuclear or polynuclear compounds.…”