Experimental Evidence of Ultrafast Quenching of the 3MLCT Luminescence in Ruthenium(II) Tris-bipyridyl Complexes via a 3dd State
Journal of the American Chemical Society2013Vol. 135(37), pp. 13660–13663
Citations Over TimeTop 10% of 2013 papers
Qinchao Sun, Sandra Mosquera‐Vázquez, Latévi Max Lawson Daku, Laure Guénée, Harold A. Goodwin, Eric Vauthey, Andreas Hauser
Abstract
Ultrafast transient absorption spectroscopy serves to identify the (3)dd state as intermediate quencher state of the (3)MLCT luminescence in the non-luminescent ruthenium complexes [Ru(m-bpy)3](2+) (m-bpy = 6-methyl-2,2'-bipyridine) and [Ru(tm-bpy)3](2+) (tm-bpy = 4,4',6,6'-tetramethyl-2',2'-bipyridine). For [Ru(m-bpy)3](2+), the population of the (3)dd state from the (3)MLCT 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' positions of bipyridine stabilize the (3)dd state by ~4000 cm(-1) each, compared to [Ru(bpy)3](2+).
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