Excited State Dynamics of Isocyano Rhenium(I) Phenanthroline Complexes from Time‐Resolved Spectroscopy

The photophysical processes in a series of isocyano Re(I) phenanthroline complexes {[Re(CNR)n(CO)4‐n(phen)](PF6); n=2, 3, 4, R=2,6‐(iPr)2C6H3‐ or tBu‐ (n=2)} in acetonitrile have been studied by resonance Raman spectroscopy, transient resonance Raman spectroscopy, and femtosecond / nanosecond transient spectroscopy to elucidate the nature of their electronic transitions and emissive excited state(s). The kinetics of the intersystem crossing, vibrational relaxation and radiative decay of the metal‐to‐ligand charge transfer {MLCT [dπ(Re)→π*(phen)]} excited state have also been determined. Excited state dynamics of a series of isocyano Re(I) phenanthroline complexes have been studied by vibrational and time‐resolved spectroscopy to elucidate the nature of their electronic transitions and emissive excited state. The kinetics of the intersystem crossing, vibrational relaxation, and radiative decay of the MLCT [dπ(Re)→π*(phen)] excited state have also been determined.