Uranyl-copper(II) heterometallic oxalate complexes: coordination polymers and frameworks

作者：Thuery Pierre^*; Riviere Eric

来源：Dalton Transactions, 2013, 42(29): 10551-10558.

DOI：10.1039/c3dt51020d

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)(2)Cu-2(C2O4)(2)(bipym)(3)(OH)(2)]center dot 2NO(3) (3) is a two-dimensional assembly in which uranyl oxalate chains are linked to one another by [Cu-2(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.

• 出版日期2013
• 单位中国地震局