Density functional theory has been performed on the calix[4]pyrrole substituted by tricyanoethylene and its complexes with the anions(F-、Cl-、CH3COO-、H2PO4-). It was shown that the host and anions could form complexes by intermolecular hydrogen bonds, and the order of the binding affinity for host is as follows : F-> CH3COO-> H2PO4-> Cl-, which is in good agreement with the experimental values; To contrast with the interaction between calix[4]pyrrole and F- and Cl-, the electron – withdrawing group substitution can enhance the interaction between calix[4] pyrrole and F- and Cl-. It has also been described that the different interaction between host and the anions and the effect of electron – withdrawing group substitution on host-guest interaction from geometry features, frequency analyses, NBO analyses and frontier orbital of interaction.

Key words: β-tricyanoethylene substituted calix[4]pyrrole, anion recognition, host-guest interaction, hydrogen bond