Molecular modeling studies of sulfur containing host/guest systems

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.