Enantiopure Cycloiridiated Complexes Bearing a Pentahelicenic N‐Heterocyclic Carbene and Displaying Long‐Lived Circularly Polarized Phosphorescence

A fused π-helical N-heterocyclic carbene (NHC) system was prepared and examined through its diastereoisomerically pure cycloiridiated complexes. The latter display light-green phosphorescence with unusually long lifetimes and circular polarization that depends on both the helical NHC P/M stereochemistry and the iridium Δ/Λ stereochemistry. These unprecedented features are attributed to extended π conjugation within the helical carbenic ligand and efficient helicene-NHC-Ir interaction.