Halogen Bond-Involving Self-Assembly of Iodonium Carboxylates: Adding a Dimension to Supramolecular Architecture.

We designed 0D, 1D, and 2D supramolecular assemblies made of diaryliodonium salts (functioning as double σ-hole donors) and carboxylates (as σ-hole acceptors). The association was based on two charge-supported halogen bonds (XB), which occurred between IIII sites of the iodonium cations and the carboxylate anions. The sequential introduction of the carboxylic groups in the aryl ring of the benzoic acid added a dimension to the 0D supramolecular organization of the benzoate, which furnished 1D-chained and 2D-layered structures when terephthalate and trimesate anions, correspondingly, were applied as XB acceptors. The structure-directing XB were studied using DFT calculations under periodic boundary conditions and were followed by the one-electron-potential analysis and the Bader atoms-in-molecules topological analysis of electron density. These theoretical methods confirmed the existence of the XB and verified the philicities of the interaction partners in the designed solid-state structures.

Metal-free and atom-efficient protocol for diarylation of selenocyanate by diaryliodonium salts.

We developed an atom- and reaction mass efficient strategy for the preparation of diarylselenides using iodonium salts as reactants. The developed approach allows the obtaining of diarylselenides from the corresponding trimethoxyphenyl-substituted iodonium salts via a two-step one-pot reaction sequence. The proposed metal-free methodology is based on the involvement of both iodonium aryl groups for diarylation.