Kuimova Marina K, Sun Xue Zhong, Matousek Pavel, Grills David C, Parker Anthony W, Towrie Michael, George Michael W
School of Chemistry, University of Nottingham, University Park, Nottingham, UK NG7 2RD.
Photochem Photobiol Sci. 2007 Nov;6(11):1158-63. doi: 10.1039/b705002j. Epub 2007 Aug 14.
The photophysics of fac-Re(R)(CO)(3)(CO(2)Et-dppz) (R = py (), 4-Me(2)N-py (); CO(2)Et-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 (2,100-1,800 cm(-1)) and organic ester (1,800-1,600 cm(-1)) regions. For 1, the picosecond TRIR spectra in the metal carbonyl region provided evidence for the formation of an intra-ligand IL (pi-pi) 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 (pi-pi) and MLCT excited states are formed within 2 ps of excitation. The magnitude of the nu(CO) shift in the metal carbonyl region following excitation allows the MLCT excited states to be described more precisely as a dpi(Re) -->pi (phenazine) (3)MLCT state for 1 and as a dpi(Re) -->pi (phenanthroline) (3)MLCT state for 2.
利用发光光谱和时间分辨红外（TRIR）光谱，在金属羰基（2100 - 1800 cm⁻¹）和有机酯（1800 - 1600 cm⁻¹）区域研究了面式-[Re(R)(CO)₃(CO₂Et - dppz)]⁺（R = 吡啶基（），4 - 二甲基氨基吡啶基（）；CO₂Et - dppz = 二吡啶并[3,2a:2',3'c]吩嗪 - 11 - 羧酸乙酯）的光物理性质。对于1，金属羰基区域的皮秒TRIR光谱为配体内IL（π - π）激发态的形成提供了证据，该激发态部分衰减至与金属 - 配体电荷转移（MLCT）激发态达到平衡。对于2，很明显在激发的2皮秒内IL（π - π）和MLCT激发态均形成。激发后金属羰基区域的ν(CO)位移幅度使得MLCT激发态对于1可更精确地描述为dπ(Re)→π（吩嗪）(³)MLCT态，对于2可描述为dπ(Re)→π（菲咯啉）(³)MLCT态。
