Diversity‐Oriented Construction and Interconversion of Multicavity Supermacrocycles for Cooperative Anion–π Binding

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Abstract
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 (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.
Funding Information
  • National Natural Science Foundation of China (21772203, 21761132024, 91427301, 21502200, 21521002)
  • Chinese Academy of Sciences (QYZDJ-SSW-SLH023)

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