新的杯[4]芳烃衍生物通过缔合乙腈进行自插入的X-射线衍射和密度泛函理论研究

合成和表征了一个新的杯4]芳烃衍生物，11,23-二羟亚胺甲基-25,27-二羟基-26,28-二丙氧基杯4]芳烃 (B)及其与乙腈生成的组成为B·2CH₃CN的化合物。¹H NMR显示，在B·2CH₃CN中B采取锥型构象，X-射线衍射分析确证在溶液中所发现的构象。在晶格网络中存在着B·2CH₃CN以二聚体形式的自插入现象。在B3LYP/6-311G(d)水平上计算了该自插入二聚体中的非共价相互作用能，并对基集叠加误差进行了校正。在二聚体中的B·2CH₃CN，一个CH₃CN通过与羟亚胺基形成氢键使之稳定，结合能为–5.02 kJ·mol^-1，另一个CH₃CN则通过与另一个羟亚胺基形成氢键以及与另一B·2CH₃CN中B苯环空腔间的C–H···π相互作用使之稳定，结合能分别为–14.23 kJ·mol^-1和–3.77 kJ·mol^-1。自插入的驱动能为–7.54 kJ·mol^-1。

Self‐inclusion of a New Calix[4]arene Derivative via Associated Acetonitrile: X‐ray Diffraction and Density Functional Theory Studies

A new calix4]arene derivative, 11,23‐bis(hydroxyiminomethyl)‐25,27‐dihydroxy‐26,28‐di‐n‐propoxycalix4]arene ( B ), was synthesized and a compound, with composition of B ·2CH₃CN, was fully characterized. ¹H NMR showed that B in the B ·2CH₃CN adopts a cone conformation. X‐ray diffraction analysis confirmed the conformation found in solution. In the crystal network, self‐inclusion phenomenon is present in a dimeric unit of B ·2CH₃CN via embedding each other. The noncovalent interaction energies were calculated at B3LYP/6‐311G(d) level and corrected by basis set superposition error (BSSE). In half a dimeric unit, one CH₃CN is stabilized via hydrogen bonding formed between nitrogen atom of the acetonitrile and one hydroxyimino group, with bonding energy of ?5.02 kJ·mol^?1, and the other one stabilized by hydrogen bonding formed between nitrogen atom of the acetonitrile and the other hydroxyimino group, with bonding energy of ?14.23 kJ·mol^?1, and by inclusion to hydrophobic cavity of the other half of the dimeric unit via C? H···π interaction, with bonding energy of ?3.77 kJ·mol^?1, doubling of which is a driving force for embedding two B ·2CH₃CN together.