Counterion-Induced Variations in the Dimensionality and Topology of Uranyl Pimelate Complexes
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- 作者：Pierre Thuéry ; Eric Rivière ; Jack Harrowfield
- 刊名：Crystal Growth & Design
- 出版年：2016
- 出版时间：May 4, 2016
- 年：2016
- 卷：16
- 期：5
- 页码：2826-2835
- 全文大小：880K
- 年卷期：0
- ISSN：1528-7505
文摘
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 (H2C7) 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(Me4phen)3]2[(UO2)4(C7)3(NO3)6]·CH3CN (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[UO2(C7)(NO3)]2 (2), in which the cations, assembled into dimers through argentophilic interactions, are organized in columns through π-stacking interactions. The heterometallic complex [UO2Mn(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 [NH4]2[(UO2)2(C7)3]·2H2O (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[(UO2)12(C7)7(O)4(OH)8]·2CH3CN·3H2O (5), obtained from the same preparation as 4, crystallizes as a three-dimensional (3D) framework displaying (μ3-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.