Synthesis, Photophysics, and Reverse Saturable Absorption of -Bis-cyclometalated Iridium(III) Complexes (C^N^C)Ir(R-tpy) (tpy = 2,2':6',2″-Terpyridine) with Broadband Excited-State Absorption.

Extending the bandwidth of triplet excited-state absorption in transition-metal complexes is appealing for developing broadband reverse saturable absorbers. Targeting this goal, five bis-terdentate iridium(III) complexes (-) bearing -bis-cyclometalating (C^N^C) and 4'-R-2,2':6',2″-terpyridine (4'-R-tpy) ligands were synthesized. The effects of the structural variation in cyclometalating ligands and substituents at the tpy ligand on the photophysics of these complexes have been systematically explored using spectroscopic methods (i.e., UV-vis absorption, emission, and transient absorption spectroscopy) and time-dependent density functional theory (TDDFT) calculations. All complexes exhibited intensely structured π,π* absorption bands at <400 nm and broad charge transfer (CT)/π,π* transitions at 400-600 nm. Ligand structural variations exerted a very small effect on the energies of the CT/π,π* transitions; however, they had a significant effect on the molar extinction coefficients of these absorption bands. All complexes emitted featureless deep red phosphorescence in solutions at room temperature and gave broad-band and strong triplet excited-state absorption ranging from the visible to the near-infrared (NIR) spectral regions, with both originating from the π,π*/CT states. Although alteration of the ligand structures influenced the emission energies slightly, these changes significantly affected the emission lifetimes and quantum yields, transient absorption spectral features, and the triplet excited-state quantum yields of the complexes. Except for , the other four complexes all manifested reverse saturable absorption (RSA) upon nanosecond laser pulse excitation at 532 nm, with the decreasing trend of RSA following ≈ > > > . The RSA trend corresponded well with the strength of the excited-state and ground-state absorption differences (ΔOD) at 532 nm for these complexes.