Tuning Photophysical and Electrochemical Properties of Heteroleptic Cationic Iridium(Ⅲ) Complexes Containing Substituted 2-Phenylquinoxaline and Biimidazole

Design and syntheses of four red phosphorescent heteroleptic cationic iridium(Ⅲ) complexes containing two substituted phenylquinoxaline (pqx) or benzo[b]thiophen-2-yl-pyridin (btp) main ligands and one 2,2'-biimidazole (H₂biim) ancillary ligand are reported: [(pqx)₂Ir(biim)]Cl (1), [(dmpqx)₂Ir(biim)]Cl (2), [(dfpqx)₂Ir(biim)]Cl (3), [(btp)₂Ir(biim)]Cl (4). Complex 1 showed a distorted octahedral geometry around the iridium(Ⅲ) metal ion with cis metallated carbons and trans nitrogen atoms. The absorption, emission and electrochemical properties were systematically evaluated. The complexes exhibited red phosphorescence in the spectral range of 580 to 620 ㎚ with high quantum efficiencies of 0.58 - 0.78 in both solution and solid-state at room temperature depending on the cyclometalated main ligands. The cyclic voltammetry of the complexes (1-3) showed a metal-centered irreversible oxidation in the range of 1.40 to 1.90 V as well as two quasi reversible reduction waves from -1.15 to -1.45 V attributed to the sequential addition of two electrons to the more electron accepting heterocyclic portion of two distinctive cyclometalated main ligands, whereas complex 4 showed a reversible oxidation potential at 1.24 V and irreversible reduction waves at -1.80 V.