Macrocycle-Directed Construction of Tetrahedral Anion-π Receptors for Nesting Anions with Complementary Geometry
Macrocycle-Directed Construction of Tetrahedral Anion-π Receptors for Nesting Anions with Complementary Geometry
复制标题
具有互补几何形状的嵌套阴离子四面体阴离子受体的大环定向构建
DOI：
10.1002/chem.201903272
复制
发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Wang De-Xian
中科院分区：
文献类型：
--
作者：
Luo Jian;Zhu Jun;Tuo De-Hui;Yuan Qinqin;Wang Lei;Wang Xue-Bin;Ao Yu-Fei;Wang Qi-Qiang;Wang De-Xian
通过复杂的主体设计以高度合作的方式操纵新兴的阴离子-π相互作用是一项非常具有挑战性的任务。在这项工作中，前所未有的四面体阴离子-π受体已被成功地构建为四面体和相关阴离子的互补调节。该合成是通过大环导向的方法通过使用带有四个反应位点的大环前体来实现的，这使得动力学有利的途径成为可能，并且以相当大的产率提供了否则不可接近的四面体笼。晶体结构表明，四面体笼具有封闭的三维空腔，由四面体阵列中的四个缺电子三嗪面包围。通过ESI-MS和DFT计算，揭示了BF 4-、ClO 4-、H2 PO 4-、HSO 4-、SO 42-和PF 6-等四面体阴离子的互补调节作用。ClO 4-和PF 6-复合物的晶体结构表明，阴离子被很好地包裹在四面体腔中，通过出色的形状和尺寸匹配，具有高达四重的阴离子-π相互作用。通过负离子光电子能谱测量进一步证实了强阴离子-π结合。
Manipulation of the emerging anion–π interactions in a highly cooperative manner through sophisticated host design represents a very challenging task. In this work, unprecedented tetrahedral anion–π receptors have been successfully constructed for complementary accommodation of tetrahedral and relevant anions. The synthesis was achieved by a macrocycle‐directed approach by using large macrocycle precursors bearing four reactive sites, which enabled a kinetic‐favored pathway and afforded the otherwise inaccessible tetrahedral cages in considerable yields. Crystal structure suggested that the tetrahedral cages have an enclosed three‐dimensional cavity surrounded by four electron‐deficient triazine faces in a tetrahedral array. The complementary accommodation of a series of tetrahedral and relevant anions including BF4−, ClO4−, H2PO4−, HSO4−, SO42−and PF6−was revealed by ESI‐MS and DFT calculations. Crystal structures of ClO4−and PF6−complexes showed that the anion was nicely encapsulated within the tetrahedral cavity with up to quadruple cooperative anion–π interactions by an excellent shape and size match. The strong anion–π binding was further confirmed by negative ion photoelectron spectroscopy measurements.