The synergistic regulation of the multi‐functional sites on one receptor molecule with different cationic effectors for anion recognition is scarce to be well understood from the experiment and theory. In this work, a new anion receptor with three functional zones including ether hole, biurea and double bipyridine groups (EUPR) is designed expecting to enhance the chloride anion recognition together with a rational synthesis path being proposed based on four simple and mature organic reaction steps. The conformational structures of the designed receptor EUPR and the binding behaviors for three kinds of ions (Cl−, Na+, and Ag+) are deeply investigated by using density functional theoretical calculations. It is found that Cl− binding via the hydrogen bond interaction can be significantly enhanced and synergistically regulated by the two kinds of cations and the corresponding conformational changes of receptor EUPR. Especially, the conformational pre‐organization of receptor caused by the encapsulation of sodium ion into ether hole is benefit to the binding for Cl− in both thermodynamics and kinetics. Na+ binding, in turn, can ever be enhanced by chloride anion, whereas it seems that Ag+ binding cannot always be enhanced by chloride anion, reflecting an electrical complementary matching and mutual enhancement effect for different counter ions. Moreover, solvent effect calculations indicate that EUPR may be an ideal candidate structure for Cl− recognition by strategy of counter ion enhancement in water. Additionally, a visual study of intermolecular noncovalent interaction (NCI) and molecular electrostatic potential (ESP) are used for the analysis on the nature of interactions between receptor and bound ions.

中文翻译：

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使用具有两种不同阳离子效应子的三功能位点受体协同调节氯阴离子识别

实验和理论还很难充分理解一种受体分子上的多功能位点与不同阳离子效应物对阴离子识别的协同调节。在这项工作中，设计了一种具有醚孔、联脲和双联吡啶基团（EUPR）三个功能区的新型阴离子受体，期望增强氯阴离子的识别，并基于四个简单且成熟的有机反应步骤提出了合理的合成路径。 。设计的受体EUPR的构象结构以及与三种离子（Cl-, 钠+，和银+）通过使用密度泛函理论计算进行了深入研究。结果发现，Cl-两种阳离子以及受体EUPR相应的构象变化可以显着增强和协同调节通过氢键相互作用的结合。特别是钠离子被醚孔包裹而引起的受体构象预组织有利于Cl的结合。-在热力学和动力学中。钠+反过来，氯阴离子可以增强结合，而 Ag 似乎+氯阴离子并不总是能增强结合，反映了不同反离子的电互补匹配和相互增强效应。此外，溶剂效应计算表明 EUPR 可能是 Cl 的理想候选结构-通过水中反离子增强策略进行识别。此外，分子间非共价相互作用（NCI）和分子静电势（ESP）的可视化研究用于分析受体和结合离子之间相互作用的性质。