Molecular modeling calculations represent an important tool to study supram
olecular host/guest systems and to deduce structure-reactivity relationship
s. In order to find optimum computer modeling approaches for describing the
structure of both macrocyclic and structure related open-chain thio ethers
and their metal complexes with Ag-I and Hg-II different modeling methods a
re tested for 1,4,7-trithiacyclononane 1, 1,3-dithiol anellated thiacrown d
erivatives 2 and bis (phenoxyalkyl)sulfane type 3 compounds. The results ar
e compared among each other and with experimental results of X-ray structur
e analysis and complexation studies using liquid-liquid extraction techniqu
e. As an aim this report should give general information and hints for the
use of molecular modeling calculations in the field of supramolecular chemi
stry and stimulate further investigations. The studies discussed show clear
ly the excellent performance of the density functional theory with the grad
ient corrected Becke-Perdew functional BP86 in the ADF package for the mode
ling of the investigated systems. The results are in each case as accurate
as can be obtained experimentally.