Wallin Staffan, Davidsson Jan, Modin Judit, Hammarström Leif
Department of Physical Chemistry, Uppsala University, Box 579, SE-75123 Uppsala, Sweden.
J Phys Chem A. 2005 Jun 2;109(21):4697-704. doi: 10.1021/jp0509212.
It is known that the relaxed excited state of [Ru(bpy)3]2+ is best described as a metal to ligand charge transfer (MLCT) state having one formally reduced bipyridine and two neutral. Previous reports have suggested [Malone, R. et al. J. Chem. Phys. 1991, 95, 8970] that the electron "hops" from ligand to ligand in the MLCT state with a time constant of about 50 ps in acetonitrile. However, we have done transient absorption anisotropy measurements indicating that already after one picosecond the molecule has no memory of which bipyridine was initially photoselected, which suggests an ultrafast interligand randomization of the MLCT state.
已知[Ru(bpy)₃]²⁺的弛豫激发态最好描述为一种金属到配体的电荷转移（MLCT）态，其中一个联吡啶形式上被还原，另外两个为中性。先前的报道[马龙，R.等人，《化学物理杂志》，1991年，95卷，8970页]表明，在乙腈中，处于MLCT态的电子从一个配体“跳跃”到另一个配体的时间常数约为50皮秒。然而，我们进行了瞬态吸收各向异性测量，结果表明，在仅仅一皮秒之后，分子就不再记得最初光选择的是哪个联吡啶，这表明MLCT态存在超快速的配体间随机化。
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