SECONDARY BONDING AS A FORCE DICTATING STRUCTURE AND SOLID-STATE AGGREGATION OF THE PRIMARY NITRENE SOURCES (ARYLSULFONYLIMINO)IODOARENES (ARINSO2AR')

Iodonium ylides of the form ArINSO2Ar' (Ar = m-tolyl, Ar' = p-nitrophe nyl (1); Ar = m-tolyl, Ar' = phenyl (2); Ar = m-tolyl, Ar' = p-tolyl ( 3); Ar, Ar' = p-tolyl (4)) have been prepared and crystallographically characterized. Comparisons to previously structurally characterized m embers of this class of materials (PhINTs (Ts = p-toluenesulfonyl), a- TolylINTs, MesINTs) demonstrate that apparently minor perturbations of the aromatic rings have substantial consequences on the supramolecula r assemblies of these materials. The structures range from zig-zag pol ymers (PhINTs, MesINTs), linear polymers (o-TolylINTs), layered struct ures (BI, two-dimensional ladders (2, 3, o-TolylINTs), to even three-d imensional stepladders (4). Ab initio calculations for a model molecul e, PhINSO2-Ph, corroborate the presence of a I-N single band and show considerable charges being localized on the I, N, S, and O atoms (+, - , +, and - charges, respectively). Extensive attractive networks of I ... O and I ... N secondary bonds thus dominate the solid-state polyme rs. Within the monomeric units of ArINSO2Ar', a U-turn-shaped motif is observed. This structural shape appears to optimize secondary bonding contacts between charged INSO2 arrays. The structures of ArINSO2Ar' h ave been systematically characterized.