Non-covalent interactions between ions and π systems play an important role in molecular recognition, catalysis and biology. To guide the screen and design for artificial hosts, catalysts and drug delivery, understanding the physical nature of ion–π complexes via descriptors is indispensable. However, even with multiple descriptors that contain the leading term of electrostatic and polarized interactions, the quantitative description for the binding energies (BEs) of ion–π complexes is still lacking because of the intrinsic shortcomings of the commonly used descriptors. Here, we have shown that the impartment of orbital details into the electrostatic energy (coined as OEE) makes an excellent single descriptor for BEs of not only spherical, but also multiply-shaped, ion–π systems, highlighting the importance of an accurate description of the electrostatic interactions. Our results have further demonstrated that OEEs from a low-level method could be calibrated to BEs from a high-level method, offering a powerful practical strategy for an accurate prediction of a set of ion–π interactions.

中文翻译：

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离子-π相互作用的准确单一描述符

离子与π系统之间的非共价相互作用在分子识别、催化和生物学中起着重要作用。为了指导人工宿主、催化剂和药物输送的筛选和设计，通过描述符了解离子-π 复合物的物理性质是必不可少的。然而，即使有包含静电和极化相互作用主导项的多个描述符，由于常用描述符的内在缺陷，仍然缺乏对离子-π配合物的结合能（BE）的定量描述。在这里，我们已经表明，将轨道细节传递给静电能量（称为 OEE）为不仅是球形的 BE 还具有多重形状的离子-π 系统提供了一个极好的单一描述符，强调准确描述静电相互作用的重要性。我们的结果进一步证明，低级方法的 OEE 可以校准为高级方法的 BE，为准确预测一组离子-π 相互作用提供了强大的实用策略。