Laser studies of radiationless decay mechanisms in Os/sup 2 +///sup 3 +/ polypyridine complexes

The lowest energy excited states in Os(II) polypyridine complexes are of a metal-to-ligand charge transfer (MLCT) type and live for 10 to 40 ..mu..s at 4.2/sup 0/K. The long wavelength absorptions in the visible region of the spectrum in Os(III) polypyridine complexes arise from ligand-to-metal charge transfer (LMCT) transitions and do not produce detectable luminescence. This suggests that these LMCT states are very short lived. Results of picosecond absorption studies on the lifetimes the LMCT states in OsL/sub 3//sup 3 +/ complexes (L = 2,2'-bipyridine(bpy) or 1,10-phenanthroline(phen)) as functions of temperature and isotopic substitution are reported. The LMCT lifetimes at low temperature are contrasted with the low temperature lifetimes of the MLCT states of OsL/sub 3//sup 2 +/ complexes and both are examined from the perspective of a coarse-grained radiationless decay theory developed by Englman, R. and Jortner, J. (Molec. Phys. 1970, 18, 145). The agreement between experiment and theory suggests the following: (1) Englman and Jortner's theory of radiationless decay is useful for inorganic as well as organic systems; (2) mid-frequency (1300 to 1600 cm/sup -1/) vibrations are the important energy accepting modes for radiationless decay of the charge transfer excited states of OsL/sub 3//sup 2 +///sup 3 +/ complexes and; (3) the 10/sup 5/-10/sup 6/ difference in lifetimes between the MLCT states of OsL/sub 3//sup 2 +/ complexes and the LMCT states of OsL/sub 3//sup 3 +/ complexes is largely due to the difference in their energy gaps