The first molecular capsule based on an [Ir(ppy)(2)](+) unit (ppy = 2-phenylatopyridine) has been prepared. Following development of a method to resolve rac-[(Ir(ppy)(2)Cl)(2)] into its enantiopure forms, homochiral Ir6L4 octahedra where obtained with the. tritopic 1,3,5-tricyanobenzene. Solution studies and X-ray diffraction show that-these capsules;encapsulate four of the six associated counteranions and that these can be exchanged for other anionic guests Initial photophysical studies have shown that an ensemble of weakly. coordinating ligands can lead to luminescence not present in comparable mononuclear systems.