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首页> 外文期刊>Chemistry: A European journal >Redox-Switchable Direction of Photoinduced Electron Transfer in an Ru(bpy)_3~(2+)-Viologen Dyad
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Redox-Switchable Direction of Photoinduced Electron Transfer in an Ru(bpy)_3~(2+)-Viologen Dyad

机译：Ru（bpy）_3〜（2 +）-紫精染料中光诱导电子转移的氧化还原可切换方向

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摘要

Quenching of the ~3MLCT excited state of [Ru(bpy)_3]~(2+) (bpy = bipyridine) by the reduction products (MV~((centre dot)+) and MV~0) of methyl viologen (MV~(2+)) was studied by a combination of electrochemistry with laser flash photolysis or femtosecond pump-probe spectroscopy. Both for the bimolecular reactions and for the reactions in an Ru(bpy)_3~(2+)-MV~(n+) dyad, quenching by (MV~((centre dot)+) and MV~0 is reductive and gives the reduced ruthenium complex [Ru(bpy)_3]~+, in contrast to the oxidative quenching by MV~(2+). Rate constants of quenching (k_q), and thermal charge recombination (k_(rec)) and cage escape yields (#PHI#_(ce)) were determined for the bimolecular reactions, and rates of for-ward (k_f) and backward (k_b) electron transfer in the dyad were measured for quenching by MV~(2+), (MV~((centre dot)+, and MV~0. The reactions in the dyad are very rapid, with values up to k_f = 1.3 X 10~(12) s~(-1) for Ru(bpy)_3~(2++)-MV~((centre dot)+) with a characteristically structured absorption spectrum was detected; this was generated by direct excitation of the MV~((centre dot)+) moiety both at 460 and 600 nm. The results show that the direction of photoinduced electron transfer in a Ru(bpy)_3-MV molecule can be switched by an externally applied bias.
机译：甲基紫精（MV〜（MV〜） （2+））是通过电化学与激光闪光光解法或飞秒泵浦-探针光谱法的结合进行研究的。对于双分子反应和在Ru（bpy）_3〜（2 +）-MV〜（n +）二聚体中的反应，通过（MV〜（（中心点）+）和MV〜0猝灭均具有还原性，得到与MV〜（2+）的氧化猝灭相反，钌络合物[Ru（bpy）_3]〜+降低。猝灭的速率常数（k_q），热电荷重组（k_（rec））和笼逃逸率确定#PHI #_（ce））的双分子反应，并通过MV〜（2 +），（MV〜（ （中心点）+和MV〜0。在二元组中的反应非常快，对于Ru（bpy）_3〜（2 ++），其值高达k_f = 1.3 X 10〜（12）s〜（-1）。检测到具有特征结构的吸收光谱的）-MV〜（（中心点）+）;这是通过在460和600 nm处直接激发MV〜（（中心点）+）部分产生的。 Ru（bpy）_3-MV分子中光诱导电子转移的方向可以通过外部施加的偏压来切换。

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