Topological control in heterometallic metal-organic frameworks by anion templating and metalloligand design
Topological control in heterometallic metal-organic frameworks by anion templating and metalloligand design
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DOI：
10.1021/ja0645483
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发表时间：
2006-11-29
影响因子：
15
通讯作者：
Cohen, Seth M.
中科院分区：
文献类型：
--
作者：
Halper, Sara R.;Do, Loi;Cohen, Seth M.
报道了几种新的基于三（二吡咯）金属配体和Ag+盐的异金属金属有机骨架（MOFs）。系统地制备了MOFs，以考察核心金属离子、抗衡阴离子和配体结构对所得网络拓扑结构的影响。金属离子（Fe 3 + vs Co 3+）对MOF结构的影响通常被发现是可忽略的，从而允许容易地合成三金属Fe/Co/Ag网络。阴离子的选择（e.例如，在一个实施例中，发现银盐）对MOF拓扑结构具有显著影响。用AgO 3SCF 3和AgBF 4的盐制备的网络可靠地形成三维（10，3）网，而使用AgPF 6和AgSbF 6产生二维（6，3）蜂窝网。在某些情况下，如阴离子交换实验所证明的，在形成MOF时产生的拓扑结构被发现是稳健的。通过X射线晶体学证实了阴离子交换在一组罕见的明显的单晶到单晶的转变。这里提出的数据强烈表明，阴离子的配位能力并没有发挥显着的作用，在所观察到的模板效应。最后，在三（dipyrrinato）金属配体的长度的变化被发现推翻阴离子模板效应，导致专门在二维（6，3）网。这些研究为通过选择配体结构和阴离子模板效应合理设计MOF拓扑结构提供了依据。此外，结果表明，精心设计的金属配体产生的结构惊人地类似于它们的有机对应物的MOFs的能力。
Several new heterometallic metal-organic frameworks (MOFs) based on tris(dipyrrinato) metalloligands and Ag+ salts are reported. MOFs were prepared systematically to examine the effects of the core metal ion, counteranion, and ligand structure on the topology of the resultant network. The effect of the metal ion (Fe3+ vs Co3+) on MOF structure was generally found to be negligible, thereby permitting the facile synthesis of trimetallic Fe/Co/Ag networks. The choice of anion (e. g., silver salt) was found to have a pronounced effect on the MOF topology. Networks prepared with salts of AgO3SCF3 and AgBF4 reliably formed three-dimensional (10,3) nets, whereas use of AgPF6 and AgSbF6 produced two-dimensional (6,3) honeycomb nets. The topology generated upon formation of the MOF was found to be robust in certain cases, as demonstrated by anion-exchange experiments. Anion exchange was confirmed by X-ray crystallography in a rare set of apparent single-crystal-to-single-crystal transformations. The data presented here strongly suggest that the coordinative ability of the anion does not play a significant role in the observed templating effect. Finally, changes in the length of the tris(dipyrrinato) metalloligand were found to override the anion templating effect, resulting exclusively in two-dimensional (6,3) nets. These studies provide a basis for the rational design of MOF topologies by choice of ligand structure and anion templating effects. Furthermore, the results demonstrate the ability of carefully designed metalloligands to generate MOFs of structure strikingly similar to that of their organic counterparts.