Steric and Geometrical Frustration Generate Two Higher-Order CuI12L8Assemblies from a Triaminotriptycene Subcomponent

The use of copper(I) in metal–organic assemblies leads readily to the formation of simple grids and helicates, whereas higher-order structures require complex ligand designs. Here, we report the clean and selective syntheses of two complex and structurally distinct CuI12L8frameworks, 1and 2, which assemble from the same simple triaminotriptycene subcomponent and a formylpyridine around the CuItemplates. Both represent new structure types. In T-symmetric 1, the copper(I) centers describe a pair of octahedra with a common center but whose vertices are offset from each other, whereas in D3-symmetric 2, the metal ions form a distorted hexagonal prism. The syntheses of these architectures illustrate how more intricate CuI-based complexes can be prepared via subcomponent self-assembly than has been possible to date through consideration of the interplay between the subcomponent geometry and solvent and electronic effects.