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

Twelve new complexes were obtained from reaction of uranyl ions with the aliphatic dicarboxylic acids HOOC–(CH2)n−2–COOH (H2Cn; n = 7–10 and 12) under solvo-hydrothermal conditions, in the presence of 3d-block metal ions (Mn2+, Fe3+, Co2+, Ni2+, and Cu2+) and 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen). In contrast to previously reported triple-stranded helicates obtained with C92– and C122–, all these complexes crystallize as polymeric one-dimensional (1D) or two-dimensional (2D) species. [Fe(bipy)3][(UO2)2(C7)3]·3H2O (1), [Cu(phen)2]2[(UO2)3(C7)4(H2O)2]·2H2O (2), and [Cu(bipy)2]2[(UO2)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][(UO2)3(C8)3(O)]·H2O (3), [Ni(phen)3][(UO2)3(C8)3(O)]·H2O (4) and [Co(phen)3][(UO2)3(C9)3(O)]·H2O (5) contain bis(μ3-oxo)-bridged tetranuclear secondary building units, and they crystallize as deeply f...