Laboratoire de Chimie, CNRS, École Normale Supérieure de Lyon, 46, Allée d'Italie, 69364 Lyon 07, France.
Chemistry. 2011 Apr 4;17(15):4177-82. doi: 10.1002/chem.201002116. Epub 2011 Mar 4.
The heteroditopic hemicryptophane 1, which bears a tripodal anion binding site and a cation recognition site in the molecular cavity, proved to be an efficient ion-pair receptor. The hemicryptophane host binds anions selectively depending on shape and hydrogen-bond-accepting ability. It forms an inclusion complex with the Me(4)N(+) ion, which can simultaneously bind anionic species to provide anion@[1⋅Me(4)N(+)] complexes. The increased affinity of [1⋅Me(4)N(+)] for anionic species is attributed to a strong cooperative effect that arises from the properly positioned binding sites in the hemicryptophane cavity, thus allowing the formation of the contact ion pair. Density functional theory calculations were performed to analyze the Coulomb interactions of the ion pairs, which compete with the ion-dipole ones, that originate in the ion-hemicryptophane contacts.
具有三齿阴离子结合位点和分子腔中阳离子识别位点的杂穴醚 1 被证明是一种有效的离子对受体。该半穴醚主体根据形状和氢键接受能力选择性地结合阴离子。它与 Me(4)N(+) 离子形成包合物，该离子可以同时结合阴离子物种以提供阴离子@[1 ⋅ Me(4)N(+)] 配合物。[1 ⋅ Me(4)N(+)] 对阴离子物种的亲和力增加归因于来自半穴醚腔中适当定位的结合位点的强协同效应，从而允许形成接触离子对。进行了密度泛函理论计算以分析竞争离子-偶极子的离子对的库仑相互作用，这些相互作用源于离子-半穴醚接触。
