Macrocyclic thioether design by molecular modelling

Abstract Two trithiamacrocycles have been designed by molecular modelling to have preorganised endodentate sulfur donor atoms. These new macrocycles have five- and six-membered saturated heterocycles inserted into 2,5,8-trithia[9]-m-benzenophane; molecular dynamics simulations suggest that the endo forms will be rigid on a nanosecond timescale. Optimum metal-sulfur distances which the new ligands will accommodate lie between 2.76 A and 2.95 A, suggesting they will be particularly suitable for a large soft metal ion such as silver(I).