Fluorene-decorated Ir(<scp>iii</scp>) complexes: synthesis, photophysics and tunable triplet excited state properties in aggregation

Two new heteroleptic cationic Ir(III) complexes bearing benzothiazole and pyridine motifs on fluorene groups were synthesized and characterized. Complexes Ir1 and Ir2 exhibit 1π,π* transitions below 430 nm, with broad but weak metal-to-ligand and ligand-to-ligand charge transfer absorption bands above 430 nm. Both complexes possess long-lived emissions (τem = 0.37 μs for Ir1, τem = 5.41 μs for Ir2) and triplet excited states (τTA = 0.14 μs for Ir1, τTA = 6.06 μs for Ir2). Their optical properties in solution and aggregated states were also investigated. Both Ir(III) complexes exhibit aggregation-induced phosphorescence emission behavior in an acetonitrile-water mixture. As the water content increased to 90%, the emission intensities of complexes Ir1 and Ir2 increased nearly 3 times and 2.8 times, respectively. Moreover, nonlinear transmittance experiments were performed in CH3CN and a CH3CN-H2O mixture (fw = 90%), and the strength of the reverse saturable absorption (RSA) at 532 nm followed the trend: Ir2 (CH3CN) ≥ Ir1 (CH3CN) > Ir2 (CH3CN-H2O) > Ir1 (CH3CN-H2O). Abundant triplet state excitons participated in the radiative transition progress, which inhibited the RSA process. These results indicate that the fluorene-decorated Ir(III) complexes are suitable for aggregation emission and optical power limiting applications.