Rare examples of transition-metal-main-group metal heterometallic metal-organic frameworks from gallium and indium dipyrrinato complexes and silver salts: synthesis and framework variability.
Rare examples of transition-metal-main-group metal heterometallic metal-organic frameworks from gallium and indium dipyrrinato complexes and silver salts: synthesis and framework variability.
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DOI：
10.1021/ic7016159
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发表时间：
2007-11
影响因子：
4.6
通讯作者：
J. R. Stork;Van S Thoi;Seth M. Cohen
中科院分区：
文献类型：
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作者：
J. R. Stork;Van S Thoi;Seth M. Cohen
合成了新的主基团金属二吡啶配合物[M(4-pyrdpm)3]，其中M = Ga3+或In3+， 4-pyrdpm是5-（4-吡啶基）二吡啶（4-pyrdpmH）的阴离子，并通过二吡啶配合物与银(I)盐反应，将其纳入金属有机框架（mof）中。由AgOTf （OTf = O3SCF3）和AgSbF6形成的mof分别具有三维（10,3）和二维（6,3）拓扑结构。相比之下，AgPF6同时产生（10,3）和（6,3）网络拓扑结构，这表明在该系统中，PF6阴离子对模板（10,3）和（6,3）框架几乎没有偏好。这些发现更新了早期的MOF研究，该研究检查了这些阴离子在使用[Fe(4-pyrdpm)3]和[Co(4-pyrdpm)3]金属配体的模板相关异金属MOF中的作用。本文报道的所有二吡啶化合物都用单晶x射线晶体学进行了表征，包括第一个具有晶体学特征的1,2,3-未取代的自由碱二吡啶，4-pyrdpmH。
New main-group metal dipyrrinato complexes [M(4-pyrdpm)3], where M = Ga3+ or In3+ and 4-pyrdpm is the anion of 5-(4-pyridyl)dipyrrin (4-pyrdpmH), have been synthesized and incorporated into metal-organic frameworks (MOFs) by reacting the dipyrrinato complexes with silver(I) salts. MOFs formed with AgOTf (OTf = O3SCF3) and AgSbF6 gave frameworks with three-dimensional (10,3) and two-dimensional (6,3) topologies, respectively. In contrast, AgPF6 produced both (10,3) and (6,3) network topologies, suggesting that the PF6 anion has little preference for templating (10,3) versus (6,3) frameworks within this system. These findings update an earlier MOF study that examined the role of these anions in templating related heterometallic MOFs which used [Fe(4-pyrdpm)3] and [Co(4-pyrdpm)3] metalloligands. All of the dipyrrin compounds reported here have been characterized by single-crystal X-ray crystallography, including the first crystallographically characterized example of a 1,2,3-unsubstituted free-base dipyrrin, 4-pyrdpmH.