Cation recognition of thiacalix[2]thianthrene and p-tert-butylthiacalix[2]thianthrene and their conformers and complexes with Zn(II), Cd(II) and Hg(II): a theoretical investigation.

The structures of thiacalix[2]thianthrene, p-tert-butylthiacalix[2]thianthrene and their complexes with Zn(2+), Cd(2+) and Hg(2+) were obtained using B3LYP/LanL2DZ and HF/LanL2DZ calculations. The structures of the most stable conformers of thiacalix[2]thianthrene and p-tert-butylthiacalix[2]thianthrene optimized at either the B3LYP/LanL2DZ or HF/LanL2DZ level are in good agreement with their corresponding X-ray crystallographic structures. The binding energies of cations, Zn(2+), Cd(2+) and Hg(2+) to thiacalix[2]thianthrene and to p-tert-butylthiacalix[2]thianthrene conformers, and the thermodynamic properties of their associations were obtained. The relative selectivities of both thiacalix[2]thianthrene and thiacalix[2]thianthrene conformer are in same order: Zn(2+) > Hg(2+) > Cd(2+).