Self-assembled chloro-bridged metallo-prismatic cations of the general formula [M6(η5-C5Me5)6(μ3-tpt)2(μ-Cl)6]6+ (M = Rh, Ir; tpt = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine)

Two cationic pentamethylcyclopentadienyl metal-based hexanuclear complexes with trigonal prismatic architecture have been synthesised through a two-step strategy. The dinuclear complexes [M(η5- C5Me5)(μ-Cl)Cl]2 (M = rhodium and iridium) react with 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (tpt) in dichloromethane to give the trinuclear complexes [Rh3(η5-C5Me5)3(μ3-tpt)Cl6] (1) and [Ir3(η5-C5Me5)3(μ3-tpt)Cl6] (2), respectively. Addition of silver triflate to 1 and 2 in dichloromethane connects two identical triangular panels to form the hexanuclear metallo-prismatic cations [Rh6(η5-C5Me5)6(μ3-tpt)2(μ-Cl)6]6+ (3) and [Ir6(η5-C5Me5)6(μ3-tpt)2(μ-Cl)6]6+ (4), respectively. Cations 3 and 4 have been isolated as their triflate salts and characterised by 1H NMR, IR and UV/visible spectroscopy.