Tetramine Aspect Ratio and Flexibility Determine Framework Symmetry for Zn 8 L 6 Self-Assembled Structures
Tetramine Aspect Ratio and Flexibility Determine Framework Symmetry for Zn 8 L 6 Self-Assembled Structures
复制标题
四胺长径比和柔韧性决定 Zn 8 L 6 自组装结构的骨架对称性
DOI：
10.1002/ange.202217987
复制
发表时间：
2023
影响因子：
--
通讯作者：
Davies J
中科院分区：
文献类型：
--
作者：
Davies J
我们推导出矩形四胺组装成Zn 8L 6伪立方配位笼的设计原理。由于配体面板的矩形几何形状（与正方形相反）以及每个金属中心在伪立方体的八个角处的Δ或Λ手性的可能性，许多不同的笼形非对映异构体是可能的。然而，在这项工作中研究的六种四苯胺子组分中的每一种都与锌（II）和2-甲酰基吡啶在乙腈中组装成单一的Zn 8L 6伪立方体非对映异构体。每个产物对应于四种非对映体构型之一，具有T，Th，S6或D3对称性。给定四苯胺子组分的优选非对映异构体显示取决于其纵横比和构象灵活性。对计算建模的单个面或整个伪立方体的分析提供了关于为什么观察到的非对映异构体是有利的的见解。
We derive design principles for the assembly of rectangular tetramines into Zn8L6pseudo‐cubic coordination cages. Because of the rectangular, as opposed to square, geometry of the ligand panels, and the possibility of either Δ or Λ handedness of each metal center at the eight corners of the pseudo‐cube, many different cage diastereomers are possible. Each of the six tetra‐aniline subcomponents investigated in this work assembled with zinc(II) and 2‐formylpyridine in acetonitrile into a single Zn8L6pseudo‐cube diastereomer, however. Each product corresponded to one of four diastereomeric configurations, withT,Th,S6orD3symmetry. The preferred diastereomer for a given tetra‐aniline subcomponent was shown to be dependent on its aspect ratio and conformational flexibility. Analysis of computationally modeled individual faces or whole pseudo‐cubes provided insight as to why the observed diastereomers were favored.