Self‐Assembly of Polyanions at a Metal Cation Template: Syntheses and Structures of [{Ag([18]aneS₆)}I₇]n and [Ag([18]aneS₆)]I₃

A distorted cubic lattice of I ions, in whose cavities the complex cations [Ag([18]aneS6)]+ ([18]aneS6 = 1,4,7,10,13,16-hexathiacyclooctadecane) are encapsulated, is formed in the synthesis of 1 (section of structure shown on the right). I− ions are positioned at the lattice points; one I2 molecule is located along each edge. The Ag+ ions function as a secondsphere template in the synthesis of the I polyanion.