Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions

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 : Twelve new complexes were obtained from reaction of uranyl ions with the aliphatic dicarboxylic acids HOOC−(CH 2) n−2 −COOH (H 2 Cn; n = 7−10 and 12) under solvo-hydrothermal conditions, in the presence of 3d-block metal ions (Mn 2+ , Fe 3+ , Co 2+ , Ni 2+ , and Cu 2+) and 2,2′-bipyridine (bipy) or 1,10-phenanthro-line (phen). In contrast to previously reported triple-stranded helicates obtained with C9 2− and C12 2− , all these complexes crystallize as polymeric one-dimensional (1D) or two-dimensional (2D) species. [Fe(bipy) 3 ][(UO 2) 2 (C7) 3 ]·3H 2 O (1), [Cu(phen) 2 ] 2 [(UO 2) 3 (C7) 4 (H 2 O) 2 ]·2H 2 O (2), and [Cu(bipy) 2 ] 2 [(UO 2) 2 (C9) 3 ] (6), in which the 3d cation was reduced in situ, are 1D ladderlike polymers displaying tetra-or hexanuclear rings, of sufficient width to encompass two counterions in 2 and 6. The three complexes [Co(phen) 3 ][(UO 2) 3 (C8) 3 (O)]·H 2 O (3), [Ni(phen) 3 ][(UO 2) 3 (C8) 3 (O)]·H 2 O (4) and [Co(phen) 3 ][(UO 2) 3 (C9) 3 (O)]·H 2 O (5) contain bis(μ 3-oxo)-bridged tetranuclear secondary building units, and they crystallize as deeply furrowed 2D assemblies. Depending on the nature of the counterion, C10 2− gives [Ni(bipy) 3 ][(UO 2) 2-(C10) 3 ]·2H 2 O (7), a 2D network displaying elongated decanuclear rings containing the counterions, or [Mn(phen) 3 ]-[(UO 2) 2 (C10) 3 ]·6H 2 O (8), [Co(phen) 3 ][(UO 2) 2 (C10) 3 ]·7H 2 O (9), and [Ni(phen) 3 ][(UO 2) 2 (C10) 3 ]·7H 2 O (10), which consist of 2D assemblies with honeycomb topology; the hexanuclear rings in 8−10 are chairlike and occupied by one counterion and two uranyl groups from neighboring layers. Two complexes of the ligand with the longest chain, C12 2−
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Submitted on : Monday, March 7, 2016 - 9:59:43 AM
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Pierre Thuéry, Jack Harrowfield. Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions. Inorganic Chemistry, American Chemical Society, 2016, 55, pp.2133-2145. ⟨http://dx.doi.org/10.1021/acs.inorgchem.5b02540⟩. ⟨10.1021/acs.inorgchem.5b02540⟩. ⟨cea-01283918⟩

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