Steric and Geometrical Frustration Generate Two Higher-Order Cu I 12 L 8 Assemblies 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 Cu I 12 L 8 frameworks, 1 and 2 , which assemble from the same simple triaminotriptycene subcomponent and a formylpyridine around the Cu I templates. 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 D 3 -symmetric 2 , the metal ions form a distorted hexagonal prism. The syntheses of these architectures illustrate how more intricate Cu I -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.