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首页> 外文期刊>Chemistry: A European journal >Zn-II-salphen complexes as versatile building blocks for the construction of supramolecular box assemblies
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Zn-II-salphen complexes as versatile building blocks for the construction of supramolecular box assemblies

机译：Zn-II-Salphen配合物可作为构建超分子盒组件的通用构建基块

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摘要

Zn-II-salphen complexes are readily accessible and interesting supramolecular building blocks with a large structural diversity. Higher-order supramolecular assemblies, such as molecular boxes based on a bis-Zn-II-salphen building block and various ditopic bipyridine ligands, have been constructed by means of supramolecular, coordinative Zn-II-N-pyr interactions. The use of bipyridine ligands of differing sizes enables the construction of structures with predefined box diameters. The features of the 2:2 box assemblies were investigated in detail by (variable temperature) NMR spectroscopy, UV-visible spectroscopy, NMR titrations, and X-ray crystallographic studies. The spectroscopic studies reveal a high association constant for the Zn-II-salphen-pyridyl motif, which lies in the range 10(5)-10(6) M-1. The strong interaction between the Zn-II center and pyridine donors was supported by PM3 calculations that showed a relatively high Lewis acid character of the metal center in the salphen complex. Titration curves monitored by UV-visible show a cooperative effect between the two bipyridine ligands upon complexation to the bis-Zn-II template, suggesting the formation of 2:2 complexes. The crystal structures of two supramolecular boxes have been determined. In both examples such a 2:2 assembly is present in the solid state, and the box size is different because they consist of different building blocks. Interestingly, the box assemblies line up in the solid state to form porous channels that are potentially useful in a number of applications.
机译：Zn-II-Salphen配合物很容易获得，并且是具有巨大结构多样性的有趣的超分子构件。借助于超分子，配位的Zn-II-N-pyr相互作用，已经构建了更高阶的超分子组装体，例如基于双-Zn-II-salphen结构单元的分子盒和各种双位联吡啶配体。使用不同大小的联吡啶配体使得能够构建具有预定盒直径的结构。通过（可变温度）NMR光谱，UV-可见光谱，NMR滴定和X射线晶体学研究详细研究了2：2盒组件的特征。光谱研究表明，Zn-II-沙芬-吡啶基基序具有较高的缔合常数，范围为10（5）-10（6）M-1。 Zn-II中心与吡啶供体之间的强相互作用得到了PM3计算的支持，而PM3计算表明，在连氮配合物中金属中心的路易斯酸特征相对较高。通过紫外-可见监测的滴定曲线显示，在与双-Zn-II模板络合后，两个联吡啶配体之间具有协同作用，表明形成了2：2的络合物。已经确定了两个超分子盒的晶体结构。在两个示例中，这样的2：2组件都以固态形式存在，并且盒子大小不同，因为它们由不同的构造块组成。有趣的是，盒子组件以固态排列，以形成可在许多应用中潜在使用的多孔通道。

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