Assembly and Disassembly of Supramolecular Hypervalent Iodine Macrocycles via Anion Coordination.

This study explores the dynamic self-assembly and disassembly of hypervalent iodine-based macrocycles (HIMs) guided by secondary bonding interactions. The reversible disassembly and reassembly of HIMs are facilitated through anion binding via the addition of tetrabutylammonium (TBA) salts or removal of the anion by the addition of silver nitrate. The association constants for HIM monomers with TBA(Cl) and TBA(Br) are calculated and show a correlation with the strength of the iodine-anion bond. A unique tetracoordinate hypervalent iodine-based compound was identified as the disassembled monomer. Last, the study reveals the dynamic bonding nature of these macrocycles in solution, allowing for rearrangement and participation in dynamic bonding chemistry.