Heterochiral vs. Homochiral Linkage of Emissive Iridium(III) Complexes with D ‐Penicillaminate: Drastic Change in Emission Induced by Silver(I) Linkage

Reactions of [{Ir(ppy or ppy‐CF 3 ) 2 } 2 (μ‐Cl) 2 ] {Hppy = 2‐phenylpyridine, Hppy‐CF 3 = 2‐[3,5‐bis(trifluoromethyl)phenyl]pyridine} with D ‐penicillamine ( D ‐H 2 pen) afforded emissive Ir III mononuclear complexes [Ir(ppy or ppy‐CF 3 ) 2 ( D ‐Hpen‐ N , S )] as a 1:1 mixture of the Δ D /Λ D isomers. These complexes were converted into Ir III Ag I Ir III trinuclear structures in [Ag{Ir( D ‐pen‐ N , S )(ppy or ppy‐CF 3 ) 2 }{Ir( D ‐Hpen‐ N , S )(ppy or ppy‐CF 3 ) 2 }] by treatment with AgNO 3 , which led to a drastic blueshift of the emission bands. Whereas the (ppy)Ir III Ag I Ir III complex produced the heterochiral Δ D Λ D isomer, the ppy‐CF 3 complex gave the homochiral Δ D Δ D and Λ D Λ D isomers that could completely be separated by crystallization. It was found that the quantum efficiency of the emission band for the Δ D Δ D isomer is much lower than that for the Λ D Λ D isomer.