Crystal engineering based on s-hole interactions is an emerging approach for realization of new materials with higher complexity.Neutral inorganic clusters derived from 1,2dicarba-closo-dodecaborane, substituted with-SeMe,-TeMe, and-I moieties on both skeletal carbon vertices are experimentally demonstrated herein as outstanding chalcogen-and halogen-bond donors.I np articular,t hese new molecules strongly interact with halide anions in the solid-state.T he halide ions are coordinated by one or two donor groups (m 1and m 2-coordinations), to stabilizeadiscrete monomer or dimer motifs to 1D supramolecular zigzag chains.C rucially, the observed chalcogen bond and halogen bond interactions feature remarkably short distances and high directionality. Electrostatic potential calculations further demonstrate the efficiency of the carborane derivatives,with V s,max being similar or even superior to that of reference organic halogen-bond donors,s uch as iodopentafluorobenzene.

A 1 : 1 metallic charge-transfer salt is obtained by cosublimation of (Z,E)-(SMe)2Me2TTF and TCNQ.