Selective Anion Binding Drives the Formation of Ag(I)(8)L(6) and Ag(I)(12)L(6) Six-Stranded Helicates

[Image: see text] Here we describe the formation of an unexpected and unique family of hollow six-stranded helicates. The formation of these structures depends on the coordinative flexibility of silver and the 2-formyl-1,8-napthyridine subcomponent. Crystal structures show that these assemblies are held together by Ag(4)I, Ag(4)Br, or Ag(6)(SO(4))(2) clusters, where the templating anion plays an integral structure-defining role. Prior to the addition of the anionic template, no six-stranded helicate was observed to form, with the system instead consisting of a dynamic mixture of triple helicate and tetrahedron. Six-stranded helicate formation was highly sensitive to the structure of the ligand, with minor modifications inhibiting its formation. This work provides an unusual example of mutual stabilization between metal clusters and a self-assembled metal–organic cage. The selective preparation of this anisotropic host demonstrates new modes of guiding selective self-assembly using silver(I), whose many stable coordination geometries render design difficult.