Ultrafast Relaxation Dynamics of Osmium-Polypyridine Complexes in Solution

We present steady-state absorption and emission spectroscopy and femtosecond broadband photoluminescence up-conversion spectroscopy studies of the electronic relaxation of Os(dmbp)(3) (Os1) and Os(bpy)(2)(dpp) (Os2) in ethanol, where dmbp is 4,4'-dimethyl-2,2'-biypridine, bpy is 2,2'-biypridine, and dpp is 2,3-dipyridyl pyrazine. In both cases, the steady-state phosphorescence is due to the lowest (MLCT)-M-3 state, whose quantum yield we estimate to be <= 5.0 x 10(-3). For Os1, the steady-state phosphorescence lifetime is 25 ns. In both complexes, the photoluminescence excitation spectra map the absorption spectrum, pointing to an excitation wavelength-independent quantum yield. The ultrafast studies revealed a short-lived (<= 100 fs) fluorescence, which stems from the lowest singlet metal-to-ligand-charge-transfer ((MLCT)-M-1) state and decays by intersystem crossing to the manifold of (MLCT)-M-3 states. In addition, Os1 exhibits a 50 ps lived emission from an intermediate triplet state at an energy similar to 2000 cm(-1) above that of the long-lived (25 ns) phosphorescence. In Os2, the (MLCT)-M-1-(MLCT)-M-3 intersystem crossing is faster than that in Os1, and no emission from triplet states is observed other than the lowest one. These observations are attributed to a higher density of states or a smaller energy spacing between them compared with Os1. They highlight the importance of the energetics on the rate of intersystem crossing.