Nonlinear Absorbing Platinum(II) Diimine Complexes: Synthesis, Photophysics, and Reverse Saturable Absorption

A series of platinum(II) diimine complexes with different sub-stituents on fluorenyl acetylide ligands (1a-1e) were synthesized and characterized. The influence of the auxiliary substituent on the photophysics of these complexes has been systematically investigated spectroscopically and theoretically (using density functional theory (DFT) methods). All complexes exhibit ligand-centered (1)pi,pi* transitions in the UV and blue spectral region, and broad, structureless (MLCT)-M-1/(LLCT)-L-1 (1a, 1b, 1d and 1e) or (MLCT)-M-1/(LLCT)-L-1/(1)pi,pi* (1c) absorption bands in the visible region. All complexes are emissive in solution at room temperature, with the emitting state is tentatively assigned to mixed (MLCT)-M-3/(3)pi,pi* states. The degree of (3)pi,pi* and (MLCT)-M-3 mixing varies with different substituents and solvent polarities. Complexes 1a-1e exhibit relatively strong singlet and triplet transient absorption from 450 to 800 nm, at which point reverse saturable absorption (RSA) could occur. Nonlinear transmission experiments at 532 nm by using nanosecond laser pulses demonstrate that 1a-1e are strong reverse saturable absorbers and could potentially be used as broadband nonlinear absorbing materials.