Strong σ-Hole Activation on Icosahedral Carborane Derivatives for a Directional Halide Recognition.

摘要: Crystal engineering based on σ -hole interactions is an emerging approach for realization of new materials with higher complexity. Neutral inorganic clusters derived from 1,2-dicarba- closo -dodecaborane, substituted -SeMe, -TeMe, and -I moieties both skeletal carbon vertices are experimentally demonstrated here as outstanding chalcogen- halogen-bond donors. In particular, these molecules strongly interact halide anions in the solid-state. The ions coordinated by one or two donor groups ( μ 1 - 2 -coordinations), to stabilize a discrete monomer dimer motifs 1D supramolecular zig-zag chains. Crucially, observed chalcogen bond halogen feature remarkably short distances strong directionality. Electrostatic potential calculations further demonstrate efficiency carborane derivatives, V s,max being similar even superior that reference organic donors such iodopentafluorobenzene.