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

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(PO3C...

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Bibliographic Details
Published in:Inorganic chemistry 2008-06, Vol.47 (12), p.5177-5183
Main Authors: Alsobrook, Andrea N, Zhan, Wei, Albrecht-Schmitt, Thomas E
Format: Article
Language:English
Subjects:
Crystal structure
Emission
Fluorescence
Formations
Ligands
Phosphonates
Sodium hydroxide
Three dimensional
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Summary: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.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic800192r