Abstract

The solvothermal synthesis and characterization of a three-dimensional, interpenetrated uranyl dicyanoaurate coordination polymer, K2(UO2)2(UO2)2(Au(CN)2)2(O)2(NO3)4, from UO2(NO3)2·6H2O and KAu(CN)2 is described. The structure contains a three-dimensional (3D) lattice of planar tetranuclear uranyl–oxo–nitrate clusters connected by dicyanoaurate linkers, with the rotation of the clusters providing the increased dimensionality. The material undergoes a reversible single-crystal to single-crystal transformation on exposure to water vapour, which is taken up in the channels of the 3D system. A second uranyl dicyanoaurate coordination polymer of the form [UO2(DMSO)3(H2O)(Au(CN)2)][Au(CN)2] was structurally characterized as a linear chain of dicyanoaurate units connected by gold–gold bonds with pendant uranyl–water–DMSO adducts that are hydrogen bonded into a two-dimensional sheet. Both materials exhibit emission arising from both the uranyl moiety and the gold(I) centre and represent the first multidimensional uranyl–dicyanoaurate coordination polymers.

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