The photophysical behavior of Re(I) diimine tricarbonyl L complexes (L= monodentate ligand) is typically dominated by population and relaxation of metal-to-ligand charge transfer excited states. Picosecond time resolved uv-vis spectra of the complex [Re(bpy)(CO)3(DMABN)]+ (DMABN = 4-dimethyl-aminobenzonitrile) suggested the complex reacts intramolecularly upon photoexcitation to form [Re(bpy-)(CO)3(DMABN+)]+ in polar protic solvents, but a long lived MLCT state was dominant in chlorocarbon solvents. We have employed ultrafast time resolved infrared spectroscopy to examine the photophysical behavior of this complex and a series of related Re(I) diimine tricarbonyl complexes. The presentation will focus on analysis of transient spectral changes of carbonyl, nitrile and aryl stretching modes and associated intramolecular charge transfer processes, including solvent effects on transient spectra and dynamics.  Time dependent density functional calculations are employed to provide insight into the observed behavior.

Photoinduced intramolecular electron transfer vs. interligand charge transfer in Re(I) diimine carbonyl complexes with electron donating monodentate ligands: Observations from ultrafast infrared results

245th National Meeting (2013)

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