Probing intraligand and charge transfer excited states of fac-[Re(R)(CO)3(CO2Et-dppz)]+ (R = py, 4-Me2N-py; CO2Et-dppz = dipyrido[3,2a:2′,3′c]phenazine-11-carboxylic ethyl ester) using time-resolved infrared spectroscopy

Photochemical & Photobiological Sciences - Tập 6 - Trang 1158-1163 - 2007
Marina K. Kuimova1, Xue Zhong Sun1, Pavel Matousek2, David C. Grills1, Anthony W. Parker2, Michael Towrie2, Michael W. George1
1School of Chemistry, University of Nottingham, University Park, Nottingham, UK
2Central Laser Facility, CCLRC Rutherford Appleton Laboratory, Oxfordshire, UK

Tóm tắt

The photophysics of fac-[Re(R)(CO)3(CO2Et-dppz)]+ (R = py (1), 4-Me2N-py (2); CO2Et-dppz = dipyrido[3,2a:2′,3′c]phenazine-11-carboxylic ethyl ester) was studied with luminescence spectroscopy and time-resolved infrared (TRIR) spectroscopy in the metal carbonyl (2100–1800 cm−1) and organic ester (1800–1600 cm−1) regions. For 1, the picosecond TRIR spectra in the metal carbonyl region provided evidence for the formation of an intra-ligand IL (π–π*) excited state, which partially decays to an equilibrium with the metal-to-ligand charge transfer (MLCT) excited state. For 2 it is evident that both IL (π–π*) and MLCT excited states are formed within 2 ps of excitation. The magnitude of the ν(CO) shift in the metal carbonyl region following excitation allows the MLCT excited states to be described more precisely as a dπ(Re) → π*(phenazine) 3MLCT state for 1 and as a dπ(Re) → π*(phenanthroline) 3MLCT state for 2.

Tài liệu tham khảo

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