This tutorial review provides an overview of the theoretical and experimental investigations that resulted in the recognition of anion-pi interactions, i.e., non-covalent forces between electron deficient aromatic systems and anions. Several pioneering theoretical studies revealed that these interactions are energetically favorable (similar to 20 - 50 kJ mol(-1)). Anion-pi interactions are gaining significant recognition, and their pivotal role in many key chemical and biological processes is being increasingly appreciated. The design of highly selective anion receptors and channels represent important advances in this nascent field of supramolecular chemistry.
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