Homochiral Self‐Sorted and Emissive Ir III Metallo‐Cryptophanes

The racemic ligands (±)‐tris(isonicotinoyl)‐cyclotriguaiacylene (L1), or (±)‐tris(4‐pyridyl‐methyl)‐cyclotriguaiacylene (L2) assemble with racemic (Λ,Δ)‐[Ir(ppy) 2 (MeCN) 2 ] + , in which ppy=2‐phenylpyridinato, to form [{Ir(ppy) 2 } 3 (L) 2 ] 3+ metallo‐cryptophane cages. The crystal structure of [{Ir(ppy) 2 } 3 (L1) 2 ]⋅3BF 4 has MM ‐ΛΛΛ and PP ‐ΔΔΔ isomers, and homochiral self‐sorting occurs in solution, a process accelerated by a chiral guest. Self‐recognition between L1 and L2 within cages does not occur, and cages show very slow ligand exchange. Both cages are phosphorescent, with [{Ir(ppy) 2 } 3 (L2) 2 ] 3+ having enhanced and blue‐shifted emission when compared with [{Ir(ppy) 2 } 3 (L1) 2 ] 3+ .