Photoluminescence Electron-Transfer Quenching of Rhenium(I) Rectangles with Amines
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- 作者：P. Thanasekaran ; Rong-Tang Liao ; Bala. Manimaran ; Yen-Hsiang Liu ; Pi-Tai Chou ; S. Rajagopal ; Kuang-Lieh Lu
- 刊名：Journal of Physical Chemistry A
- 出版年：2006
- 出版时间：September 21, 2006
- 年：2006
- 卷：110
- 期：37
- 页码：10683 - 10689
- 全文大小：105K
- 年卷期：v.110,no.37(September 21, 2006)
- ISSN：1520-5215
文摘
Electron-transfer (ET) reactions from aromatic amines to excited states of rhenium(I)-based molecular rectangles[{Re(CO)3(
-bpy)Br}{Re(CO)3(-L)Br}]2 (bpy = 4,4'-bipyridine, L = 4,4'-dipyridylacetylene (dpa), I; L =4,4'-dipyridylbutadiyne (dpb), II; and L = 1,4-bis(4'-pyridylethynyl)benzene (bpeb), III) were investigatedin a dichloromethane solution using luminescence quenching techniques. Direct evidence for the ET reactionwas obtained from the detection of the amine cation radical in this system using time-resolved transientabsorption spectroscopy. The values of the luminescence quenching rate constants, kq, of the 3MLCT excitedstate of Re(I) rectangles with amines were found to be higher than those for the monomeric Re(I) complexesand other Re(I)-based metallacyclophanes. The observed kq values were correlated well with the drivingforce (
G
) for the ET reactions. In addition, a semiclassical theory of ET was successfully applied to thephotoluminescence quenching of Re(I) rectangles with amines.
-bpy)Br}{Re(CO)3(-L)Br}]2 (bpy = 4,4'-bipyridine, L = 4,4'-dipyridylacetylene (dpa), I; L =4,4'-dipyridylbutadiyne (dpb), II; and L = 1,4-bis(4'-pyridylethynyl)benzene (bpeb), III) were investigatedin a dichloromethane solution using luminescence quenching techniques. Direct evidence for the ET reactionwas obtained from the detection of the amine cation radical in this system using time-resolved transientabsorption spectroscopy. The values of the luminescence quenching rate constants, kq, of the 3MLCT excitedstate of Re(I) rectangles with amines were found to be higher than those for the monomeric Re(I) complexesand other Re(I)-based metallacyclophanes. The observed kq values were correlated well with the drivingforce (G) for the ET reactions. In addition, a semiclassical theory of ET was successfully applied to thephotoluminescence quenching of Re(I) rectangles with amines.