Covalent macrocycles and three-dimensional cages were prepared by the self-assembly of di- or tritopic anilines and 2,6-diformylpyridine subcomponents around palladium(II) templates. The resulting 2,6-bis(imino)pyridyl-PdII motif contains a tridentate ligand, leaving a free coordination site on the PdII centers, which points inward. The binding of ligands to the free coordination sites in these assemblies was found to alter the product stability, and multitopic ligands could be used to control product size. Multitopic ligands also bridged metallomacrocycles to form higher-order supramolecular assemblies, which were characterized via NMR spectroscopy, mass spectrometry, and X-ray crystallography. An efficient method was developed to reduce the imine bonds to secondary amines, leading to fully organic covalent macrocycles and cages that were inaccessible through other means.

中文翻译：

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金属和有机模板共同控制共价大环化合物和笼子的大小

共价大环和三维笼是通过二元或三元苯胺和 2,6-二甲酰基吡啶亚组分围绕钯 (II) 模板自组装制备的。得到的 2,6-双（亚氨基）吡啶基-PdII 基序包含一个三齿配体，在 PdII 中心留下一个自由配位点，指向内。发现配体与这些组件中的自由配位位点的结合会改变产品的稳定性，多主题配体可用于控制产品的大小。多主题配体还桥接金属大环以形成高阶超分子组装体，通过核磁共振光谱、质谱和 X 射线晶体学对其进行表征。开发了一种有效的方法来减少与仲胺的亚胺键，