Iodonium cation stabilizes Square-Planar configuration of the Silver(I) tetratriflate

In this work we have experimentally and theoretically shown that halogen bonding can stabilize the rare example of square-planar configuration of the silver(I) center. The crystallographic analysis of tris-dibenziodolium silver(I) tetratriflate reveals two types of halogen bonding interactions between the triflate ligands and the dibenziodolium cation, which might stabilize the such square-planar coordination geometry. Theoretical calculations confirm the noncovalent nature of the I⋅⋅⋅O contacts and provide insights into their electronic properties.