Departament de Química, Universitat de les Illes Balears, 07122 Palma de Mallorca, Spain.
Angew Chem Int Ed Engl. 2011 Oct 4;50(41):9564-83. doi: 10.1002/anie.201100208. Epub 2011 Sep 16.
Supramolecular chemistry is a field of scientific exploration that probes the relationship between molecular structure and function. It is the chemistry of the noncovalent bond, which forms the basis of highly specific recognition, transport, and regulation events that actuate biological processes. The classic design principles of supramolecular chemistry include strong, directional interactions like hydrogen bonding, halogen bonding, and cation-π complexation, as well as less directional forces like ion pairing, π-π, solvophobic, and van der Waals potentials. In recent years, the anion-π interaction (an attractive force between an electron-deficient aromatic π system and an anion) has been recognized as a hitherto unexplored noncovalent bond, the nature of which has been interpreted through both experimental and theoretical investigations. The design of selective anion receptors and channels based on this interaction represent important advances in the field of supramolecular chemistry. The objectives of this Review are 1) to discuss current thinking on the nature of this interaction, 2) to survey key experimental work in which anion-π bonding is demonstrated, and 3) to provide insights into the directional nature of anion-π contact in X-ray crystal structures.
超分子化学是一门科学探索领域,探究分子结构与功能之间的关系。它是研究非共价键的化学,非共价键是高度特异性识别、传输和调节生物过程的基础。超分子化学的经典设计原则包括氢键、卤键和阳离子-π 络合等强、方向性相互作用,以及离子配对、π-π、疏溶剂相互作用和范德华力等较弱的相互作用。近年来,阴离子-π 相互作用(缺电子芳环π体系与阴离子之间的吸引力)被认为是一种迄今尚未开发的非共价键,其性质已通过实验和理论研究进行了解释。基于这种相互作用设计选择性阴离子受体和通道是超分子化学领域的重要进展。本文的目的是:1)讨论对这种相互作用性质的现有认识;2)综述证明阴离子-π 键合的关键实验工作;3)深入了解 X 射线晶体结构中阴离子-π 接触的方向性。