Abstract
The charge transfer (CT) excited states of Ru(II)OEP(Py)2 and Ru(II)TPP(Py)2 (TPP = tetraphenylporphyrin, OEP = octaethylporphyrin, and Py = pyridine) have been investigated by nanosecond time-resolved resonance Raman (TR3) spectroscopy. The spectra reveal unexpected differences between the two species. The TR3 spectrum of [Ru(II)TPP(Py)2]* resembles the resonance Raman (RR) spectrum of the RuTPP(Py)2 radical anion. Both spectra show strong enhancement of nontotally symmetric modes, resulting from a Jahn−Teller distortion due to the eg* orbital degeneracy. The band frequencies are slightly higher in the CT state than in the radical anion, reflecting the effect of the Ru(II) oxidation. Thus, the TR3 spectral features support a 3(dπ,π*) excited state assignment, with an electron transferred from Ru(II) to the porphyrin. In contrast, the TR3 spectrum [Ru(II)OEP(Py)2]* does not resemble the RR spectra of the Ru(II)OEP radical anion. Rather, it contains totally symmetric modes, at frequencies close to those of...
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