Molecular Dynamics Simulation and Density Functional Theory Investigation for Thiacalix[4]biscrown and its Complexes with Alkali-Metal Cations

Abstract

The structural and energetic preferences of thiacalix[4]biscrown-5 with and without alkali metal ions (Na+, K+, Rb+, and Cs+) have been theoretically investigated for the first time using molecular dynamic (MD) simulations and density functional theory (MPWB1K/6-31G(d)//B3LYP/6-31G(d)) methods. The formation of the metal ion complex by the host is mainly driven by the electrostatic attraction between crown-5 oxygens and a cation together with the minor contribution of the cation-pi interaction between two facing phenyl rings around the cation. The computed binding energies and the atomic charge distribution analysis for the metal binding complexes indicate the selectivity toward a potassium ion. The theoretical results herein explain the experimentally observed extractability order by this host towards various alkali metal ions. The physical nature and the driving forces for cation recognition by this host are discussed in detail.