Experimental Evidence of Ultrafast Quenching of the 3MLCT Luminescence in Ruthenium(II) Tris-bipyridyl Complexes via a 3dd State
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- 作者：Qinchao Sun ; Sandra Mosquera-Vazquez ; Lat茅vi Max Lawson Daku ; Laure Gu茅n茅e ; Harold A. Goodwin ; Eric Vauthey ; Andreas Hauser
- 刊名：Journal of the American Chemical Society
- 出版年：2013
- 出版时间：September 18, 2013
- 年：2013
- 卷：135
- 期：37
- 页码：13660-13663
- 全文大小：295K
- 年卷期：v.135,no.37(September 18, 2013)
- ISSN：1520-5126
文摘
Ultrafast transient absorption spectroscopy serves to identify the 3dd state as intermediate quencher state of the 3MLCT luminescence in the non-luminescent ruthenium complexes [Ru(m-bpy)3]2+ (m-bpy = 6-methyl-2,2鈥?bipyridine) and [Ru(tm-bpy)3]2+ (tm-bpy = 4,4鈥?6,6鈥?tetramethyl-2鈥?2鈥?bipyridine). For [Ru(m-bpy)3]2+, the population of the 3dd state from the 3MLCT state occurs within 1.6 ps, while the return to the ground state takes 450 ps. For [Ru(tm-bpy)3]2+, the corresponding values are 0.16 and 7.5 ps, respectively. According to DFT calculations, methyl groups added in the 6 and 6鈥?positions of bipyridine stabilize the 3dd state by 4000 cm鈥? each, compared to [Ru(bpy)3]2+.