Homochiral Emissive Λ(8)‐ and Δ(8)‐[Ir(8)Pd(4)](16+) Supramolecular Cages

Synthetic self‐assembly is a powerful technique for the bottom‐up construction of discrete and well‐defined polyhedral nanostructures resembling the spherical shape of large biological systems. In recent years, numerous Archimedean‐shaped coordination cages have been reported based on the assembly of bent monodentate organic ligands containing two or more distal pyridyl rings and square‐planar Pd(II) ions. The formation of photoactive Pd(II) metallamacrocycles and cages, however, remain rare. Here we report the first examples of emissive and homochiral supramolecular cages of the form [Ir(8)Pd(4)](16+). These cages provide a suitably sized cavity to host large guest molecules. Importantly, encapsulation and energy transfer have been observed between the blue‐emitting NBu(4)[Ir(dFppy)(2)(CN)(2)] guest and the red‐emitting Δ(8)‐[Ir(8)Pd(4)](16+) cage.