Diversity-Oriented Construction and Interconversion of Multicavity Supermacrocycles for Cooperative Anion-pi Binding
Diversity-Oriented Construction and Interconversion of Multicavity Supermacrocycles for Cooperative Anion-pi Binding
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用于协同阴离子π结合的多腔超大环的多样性导向构建和相互转换
DOI：
10.1002/anie.201810836
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Wang De-Xian
中科院分区：
文献类型：
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作者：
Luo Jian;Ao Yu-Fei;Wang Qi-Qiang;Wang De-Xian
使用合理设计的大环前体实现了一种用于一系列超大环的多样性构建的一锅策略。发现该碱不仅对尺寸分布而且对形成的超大环的结构具有显著影响。虽然使用较少的CsF（<4.0当量）得到含有至多四个大环前体亚基的规则超大环，但使用更多的CsF（>8.0当量）得到结构重组的超大环，其特征在于氧杂杯[2]芳烃[2]三嗪基序。 还揭示了碱基介导的超大环到超大环的转化。具有大的空腔和许多缺电子三嗪部分，超大环可以通过多种阴离子-π相互作用容纳大的有机阴离子，如两种超大环所证明的，其可以容纳2-羧基乙酸酯，并代表具有阴离子-π相互作用的三明治状结构的第一个晶体学实例。
A one‐pot strategy for the diverse construction of a series of supermacrocycles was realized using rationally designed macrocyclic precursors. The base was found to have a significant effect not only on the size distribution but also on the structure of the supermacrocycles formed. While the use of less CsF (<4.0 equiv) afforded regular supermacrocycles containing up to four macrocyclic precursor subunits, the use of more CsF (>8.0 equiv) resulted in structurally reorganized supermacrocyles featuring oxacalix[2]arene[2]triazine motifs. Base‐mediated supermacrocycle‐to‐supermacrocycle transformations were also revealed. With large cavities and many electron‐deficient triazine moieties, the supermacrocyles can accommodate large organic anions via multiple anion–π interactions as demonstrated for two supermacrocycles, which can host 2‐carboxyacetate and represent the first crystallographic examples of sandwich‐like structures with anion–π interactions.