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Counterion-Induced Variations in the Dimensionality and Topology of Uranyl Pimelate Complexes

Abstract : The structure-directing effect of counterions with different shapes and charges has been investigated in the case of the complexes formed by uranyl ions with pimelic (heptanedioic) acid (H 2 C7) under solvo-hydrothermal conditions. Following the previously reported isolation of one-dimensional (1D) chains with the counterions [Fe(bipy) 3 ] 2+ and [Cu(phen) 2 ] + , the complex [Ni(Me 4 phen) 3 ] 2 [(UO 2) 4 (C7) 3 (NO 3) 6 ]·CH 3 CN (1), with a bulkier cation, was synthesized and shown to consist of molecular anionic tetranuclear uranyl species, the presence of coordinated nitrate ions preventing polymerization. 1D zigzag chains are formed in [Ag(bipy) 2 ] 2-[UO 2 (C7)(NO 3)] 2 (2), in which the cations, assembled into dimers through argentophilic interactions, are organized in columns through π-stacking interactions. The heterometallic complex [UO 2 Mn(C7) 2 (phen) 2 ] (3) is formed in the presence of manganese(II) cations, and it crystallizes as a two-dimensional (2D) assembly in which manganese dimers display weak antiferromagnetic coupling (J = −1.2 cm −1). Another 2D network is found in [NH 4 ] 2 [(UO 2) 2 (C7) 3 ]·2H 2 O (4), where ammonium cations are generated in situ; in this case, parallel polycatenation of the highly convoluted 2D layers generates a 3D lattice. Finally, the complex [Co(en) 3 ] 2 [(UO 2) 12 (C7) 7 (O) 4 (OH) 8 ]·2CH 3 CN·3H 2 O (5), obtained from the same preparation as 4, crystallizes as a three-dimensional (3D) framework displaying (μ 3-oxo/hydroxo)-bridged linear ribbons as secondary building units; the [Co(en) 3 ] 3+ counterions occupy channels parallel to the ribbons and are involved in numerous hydrogen bonding interactions with uranyl oxo and carboxylate groups. Complex 3 only displays intense and well-resolved emission bands under excitation at 420 nm; the emission of complexes 1, 2, and 4 is partly quenched, the maxima positions being the same as for complex 3. ■ INTRODUCTION The aliphatic α,ω-dicarboxylic acids of general formula HOOC−(CH 2) n−2 −COOH (H 2 Cn) are among the simplest polycarboxylic species which have been used in the synthesis of uranyl−organic coordination polymers and frameworks, 1−6 and they are also probably the most conformationally flexible, particularly when compared with the more common benzene-derived ones. The first to be studied were those with short chains such as succinic (n = 4) or glutaric (n = 5) acids, 7−14
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Submitted on : Monday, May 9, 2016 - 4:34:25 PM
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Pierre Thuéry, Eric Rivière, Jack Harrowfield. Counterion-Induced Variations in the Dimensionality and Topology of Uranyl Pimelate Complexes. Crystal Growth and Design, American Chemical Society, 2016, 16, pp.2826-2835. ⟨10.1021/acs.cgd.6b00156⟩. ⟨cea-01313223⟩



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