Strategic Synthesis and Supramolecular Organization of Arylenebis(aryliodonium) Salts

A comprehensive synthetic toolkit was developed for the preparation of arylenebis(aryliodonium) salts from diiodoarenes via m-CPBA oxidation. The methodology offers versatile approaches that can be adapted based on the solubility of reaction intermediates, enabling either one-pot or two-stage synthesis pathways. Four distinct synthetic methods were established, accommodating a wide range of arenes and diiodoarenes, including sterically hindered and electron-deficient substrates. The resulting bis(iodonium) salts were isolated in good to excellent yields (up to 99%). X-ray crystallographic analysis of these compounds revealed intriguing supramolecular organization in the solid state, with the formation of 1D chains through halogen bonding interactions. These self-assembled architectures demonstrate the potential of bis(iodonium) cations as valuable tectons for applications in crystal engineering.