Acta Phys. -Chim. Sin. ›› 2013, Vol. 29 ›› Issue (10): 2187-2197.doi: 10.3866/PKU.WHXB201308142


Theoretical Study of Calix[4]pyrrole Complexes with Halide and AmmoniumIons

CHEN Xue-Song1, LU Peng-Fei1, DONG Yu-Hui2, XIE Ju1   

  1. 1 School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu Province, P. R. China;
    2 Weifang University of Science and Technology, Weifang 262700, Shandong Province, P. R. China
  • Received:2013-05-21 Revised:2013-08-08 Published:2013-09-26
  • Contact: XIE Ju
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21103147).


Density functional theory M06-2X/6-31G(d, p) was used on complexes of calix[4]pyrrole (CP) with halide anions (X-=F-, Cl-, Br-) and NH4+-X- ion-pairs. Geometries, binding energies, natural bond orbital analysis, and multifunctional wave function analysis (Multiwfn) were presented in detail. The results indicated that the interaction between the calix[4]pyrrole and halide anions mainly involved hydrogen (H)-bonds. Long-range van der Waals forces and steric effects were determined in the CP-Cl- and CP-Br- systems by Multiwfn analysis. Calix[4]pyrrole forms stable complexes with NH4+-X- ion-pairs mainly through H-bonds and electrostatic interactions, as well as via cation-π interactions. The 2:1 complexes of CP and anions or ion-pairs were also considered theoretically, but 2:1 is not the dominant stoichiometry relative to the 1:1 complexes. The current study also demonstrates that calix[4]pyrrole functions not only as an anion receptor, but also as a good ion-pair receptor, especially in cases involving fluoride ions.

Key words: Calix[4]pyrrole, Anion and ion-pair, Host-guest interaction, Quantumchemistry calculation


  • O641