Abstract
Two color picosecond Raman spectroscopy has been utilized to measure interligand electron transfer in the excited MLCT states of mixed ligand Ru(II) complexes. No contribution to electron transfer was found from hot vibrational levels produced by photoexcitation. For thermally relaxed vibrational levels the first direct measurement of the upper limit to the rate of interligand electron hopping is reported. It was found that the rate from the thermally equilibrated vibrational states was ≤2×106 s−1. Low temperature Raman spectra indicate that the slow rate of electron transfer creates a nonstatistical energy distribution between dissimilar ligands. The implications of these results are discussed within the framework of electron transfer theory.
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