Controlled Halogen-Bond-Involving Assembly of Double-sigma-Hole-Donating Diaryliodonium Cations and Ditopic Arene Sulfonates

The supramolecular dimensionality of halogen bonded architectures formed in the solid state by diaryliodonium salts is greater when the anion is a disulfonate rather than a monosulfonate. Specifically, diaryliodonium cations conventionally function as double-sigma-hole halogen bond (XB) donors and form 0D-heterotetrameric motifs when paired with monosulfonate anions. Here it is reported that when 1,5- and 2,6-naphthalenedisulfonate anions are used as ditopic XB acceptors, their assemblies with diaryliodonium cations provide architectures of higher dimensionality. 1,5-Naphthalenedisulfonate leads to the occurrence of 1D chains, while the longer and less sterically encumbered 2,6-naphthalenedisulfonate produces either 1D chains or 2D layers. The two-center I center dot center dot center dot OSO supramolecular synthon is observed most frequently, and the three-center I center dot center dot center dot OSO linkage was identified in some assemblies based on 2,6-naphthalenedisulfonate.