Second-order nonlinear optical response of phenyl-substituted cationic BIS-cyclometalated iridium(III) complexes: Effect of different position

In this paper, a series of cationic iridium complexes [(2-phenylpyridine) 2 (2,2[Formula: see text]-bipyridine)Ir][Formula: see text] which substituted phenyl on different ligands position have been systematically investigated by density functional theory (DFT) method. Significantly, the first hyperpolarizability [Formula: see text] values can be enhanced by introducing phenyl on 2-phenylpyridine ligands R 1 or R 2 , whereas substituting phenyl on 2,2[Formula: see text]-bipyridine ligands R 3 result in a decreasing [Formula: see text] values. The [Formula: see text] values exhibit obvious connection with the corresponding HOMO and LUMO energy gap. Furthermore, the time-dependent (TD) DFT calculations suggest that the enhanced [Formula: see text] values are related to obvious charge transfer from 2-phenylpyridine ligands to 2,2[Formula: see text]-bipyridine ligands. The investigation of frequency-dependent first hyperpolarizability [Formula: see text] ([Formula: see text]; [Formula: see text], 0) and [Formula: see text] ([Formula: see text]; [Formula: see text], [Formula: see text]) shown less dispersion effect at the low-frequency region for all of the studied complexes. Overall, tuning phenyl on the different ligands position can be seen as an effective strategy to modulate the second-order nonlinear optical response for these iridium complexes, which is benefit to theoretical and experimental further investigation.