Tuning the Photophysical and Excited State Properties of Phosphorescent Iridium(III) Complexes by Polycyclic Unit Substitution.

Two novel N-embedded polycyclic units functionalized phosphorescent iridium(III) complexes (Ir-1 and Ir-2) with substituents in different positions have been prepared. Complex Ir-1 bearing the substituent at the 3-position shows a distinct blue shift single-peak emission (524 nm) with a higher luminescence efficiency (ΦPL=42 %) and shorter emission lifetime (τ=282 ns) by comparison with 4-position substitution based complex Ir-2 (ΦPL=23 %, τ=562 ns), which exhibits a dual-peak emission (564 nm and 602 nm), and phosphorescence color can be tuned from green to yellow. In addition, DFT calculations demonstrate that unusual ligand-to-metal charge transfer (3LMCT) excited state property can be found in Ir-2, which is in contrast to metal-to-ligand charge transfer (3MLCT) excited state character in Ir-1. This result can be attribute to strong electron-donating character and 4-position substitution effect of the unit.