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Complexation of Uranyl Ion with Sulfonates: One- to Three-Dimensional Assemblies with 1,5- and 2,7-Naphthalenedisulfonates

Pierre Thuéry 1 Jack Harrowfield 2 
1 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)
NIMBE UMR 3685 - Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M)
Abstract : Uranyl nitrate was reacted with the sodium salt of either 1,5- or 2,7-naphthalenedisulfonate (1,5-ndsNa2 and 2,7-ndsNa2, respectively) under (solvo)-hydrothermal conditions, in the presence of additional coligands and/or metal cations, to give six new complexes which were characterized by their crystal structure determinations. [UO2(1,5-nds)(H2O)] (1) crystallizes as a three-dimensional (3D) framework, with both sulfonate groups coordinated in the O,Oʹ-bridging mode. In the presence of the N-chelating species 2,2ʹ-bipyridine (bipy) or 1,10-phenanthroline (phen), the three complexes [(UO2)2(1,5-nds)(OH)2(bipy)2]H2O (2), [(UO2)2(1,5-nds)(OH)2(bipy)2]bipy (3) and [(UO2)2(1,5-nds)(OH)2(phen)2] (4) were obtained, in which doubly hydroxide-bridged uranyl dimers are assembled into one-dimensional (1D) chains by bis(unidentate) disulfonate ligands. The complex [Cu(bipy)2Cl][UO2(2,7-nds)(OH)]H2O (5) displays anionic, two-dimensional (2D) sheets in which unidentate/O,Oʹ-bridging disulfonate ligands link hydroxide-bridged uranyl dimers. In the additional presence of cucurbit[6]uril (CB6), the complex [(UO2)4Na4(2,7-nds)2(CB6)Cl4O2(H2O)10]5H2O (6) crystallizes as a 3D framework of intricate architecture, with bis(3-oxo) bridged uranyl tetranuclear moieties connected to CB6-bound sodium cations by doubly O,Oʹ-bridging disulfonates. Complexes 2 and 4 display intense and well-resolved uranyl emission in the solid state, while nearly complete quenching is observed in 3 and 5.
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Submitted on : Saturday, December 24, 2016 - 10:42:44 AM
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Pierre Thuéry, Jack Harrowfield. Complexation of Uranyl Ion with Sulfonates: One- to Three-Dimensional Assemblies with 1,5- and 2,7-Naphthalenedisulfonates. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2016, 2017, pp.979-987. ⟨10.1002/ejic.201601374⟩. ⟨cea-01422222⟩



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