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+).