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Issue 29, 2013
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Uranyl–copper(II) heterometallic oxalate complexes: coordination polymers and frameworks

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Abstract

Five oxalate complexes containing both uranyl and copper(II) ions and 2,2′-bipyridine (bipy), 2,2′-bipyrimidine (bipym) or 1,10-phenanthroline (phen) as co-ligands have been synthesized under hydrothermal conditions and their crystal structures were determined. [UO2Cu(C2O4)(NO3)2(bipy)(H2O)] (1) is a molecular complex in which the two cations are connected by the bis-chelating oxalate. A one-dimensional uranyl oxalate ribbon is formed in [UO2Cu(C2O4)2(bipym)(H2O)] (2), with uranyl ions bound to two chelating anions and to a third, monodentate oxalate which holds the decorating [Cu(bipym)(H2O)]2+ groups. Complex [(UO2)2Cu2(C2O4)2(bipym)3(OH)2]·2NO3 (3) is a two-dimensional assembly in which uranyl oxalate chains are linked to one another by [Cu2(bipym)3]4+ dinuclear units through bridging hydroxide ions. Finally, [UO2Cu(C2O4)2(bipy)] (4) and [UO2Cu(C2O4)2(phen)] (5) display identical three-dimensional arrangements containing uranyl oxalate sheets connected to one another by copper oxalate dinuclear units. The magnetic properties of compounds 2 and 4 have been investigated. Weak inter-chain antiferromagnetic interactions between copper(II) atoms are present in 2, while 4 displays strong oxalate-mediated antiferromagnetic exchange (J = −335 cm−1). These complexes are the first uranyl–d block metal oxalate complexes to be reported.

Graphical abstract: Uranyl–copper(ii) heterometallic oxalate complexes: coordination polymers and frameworks

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Publication details

The article was received on 17 Apr 2013, accepted on 23 May 2013 and first published on 12 Jun 2013


Article type: Paper
DOI: 10.1039/C3DT51020D
Citation: Dalton Trans., 2013,42, 10551-10558
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    Uranyl–copper(II) heterometallic oxalate complexes: coordination polymers and frameworks

    P. Thuéry and E. Rivière, Dalton Trans., 2013, 42, 10551
    DOI: 10.1039/C3DT51020D

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