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Counter-ion control of structure in uranyl ion complexes with 2,5-thiophenedicarboxylate †

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 : 2,5-Thiophenedicarboxylic acid (H2TDC) was reacted with uranyl nitrate under solvo-hydrothermal conditions with acetonitrile or N-methyl-2-pyrrolidone as organic co-solvents and different combinations of d-block metal ions and N-donating chelators. The complexes [NiIJbipy)3]ij(UO2)2IJTDC)2IJHTDC)IJNO3)]·NMP ·H2O (1) and [CoIJ(NH2)2sar)]ij(UO2)2IJTDC)2IJHTDC)2]·Cl·6H2O (2) (bipy = 2,2′-bipyridine, sar = sarcophagine = 3,6,10,13,16,19-hexaazabicycloij6.6.6]icosane), the latter containing the enantiomerically pure Λ-isomer of the counter-ion, crystallize as one-dimensional coordination polymers in which the TDC2− ligands are bischelating and the HTDC− ones are mono-chelating and terminal. Two-dimensional (2D) honeycomb networks with all ligands bis-chelating are generated in the two isomorphous complexes [FeIJphen)3]2ij(UO2)4IJTDC)6]ijUO2IJNMP)2IJNO3)2]·2NMP (3) and [NiIJphen)3]2ij(UO2)4IJTDC)6]ijUO2IJNMP)2IJNO3)2] ·NMP (4) (phen = 1,10-phenanthroline), while a 2D assembly with a tessellation of 4- and 8-membered rings (fes topological type) is formed in [AgIJCH3CN)3]2ij(UO2)2IJTDC)3]·H2O (5). Finally, [AgIJbipy)2]5ij(UO2)4IJTDC)6]·NO3·6H2O (6) comprises planar honeycomb networks which generate a threedimensional (3D) architecture through inclined 2D → 3D polycatenation; the [AgIJbipy)2]+ cations are assembled into columns held by π-stacking and weak argentophilic interactions, which occupy the channels formed by the intersecting layers. Complete quenching of uranyl luminescence occurs in complexes 1–4 and only 6 displays an emission spectrum in the solid state showing the usual well-resolved vibronic fine structure.
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Submitted on : Monday, March 7, 2016 - 10:02:16 AM
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Pierre Thuéry, Jack Harrowfield. Counter-ion control of structure in uranyl ion complexes with 2,5-thiophenedicarboxylate †. CrystEngComm, Royal Society of Chemistry, 2016, 18, pp.1550. ⟨10.1039/c5ce02294k⟩. ⟨cea-01283922⟩



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