Remote Control of Electron Transfer Reaction by Microwave Irradiation: Kinetic Demonstration of Reduction of Bipyridine Derivatives on Surface of Nickel Particle
Remote Control of Electron Transfer Reaction by Microwave Irradiation: Kinetic Demonstration of Reduction of Bipyridine Derivatives on Surface of Nickel Particle
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DOI：
10.1021/acs.jpclett.9b00629
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发表时间：
2019-06-20
影响因子：
5.7
通讯作者：
Wada, Yuji
中科院分区：
文献类型：
--
作者：
Kishimoto, Fuminao;Matsuhisa, Masayuki;Wada, Yuji
微波辐射具有远程控制化学反应的巨大潜力，特别是涉及电子转移的反应。在这项研究中，我们发现，还原反应的联吡啶衍生物的金属镍颗粒被加速或减速的2.45 GHz的微波没有改变的反应温度。电子转移反应的微波加速程度的顺序与联吡啶衍生物的氧化还原电位的负性一致，即，微波辐射显著增强了具有较小Δ G的电子转移。应用Marcus的电子转移理论，提出了微波作用于电子转移反应的两种机理，即，Ni粒子中电子的振动使电子转移更容易，水分子的旋转防止电子转移反应后水合体系的重组。
Microwave irradiation has great potential to control chemical reactions remotely, particularly reactions that involve electron transfer. In this study, we found that the reduction reaction of bipyridine derivatives on metal nickel particles was accelerated or decelerated by 2.45 GHz microwaves without an alteration of the reaction temperature. The order of the extent of the microwave acceleration of the electron transfer reaction coincided with the negativity of the redox potential of the bipyridine derivatives, i.e., the electron transfer with smaller Delta G was significantly enhanced by microwave irradiation. By applying Marcus' electron transfer theory, we propose two mechanisms of the microwave effect on electron transfer reactions, i.e., vibration of the electrons in Ni particles to make the electron transfer easier and rotation of the water molecules to prevent the reorganization of the hydrated systems after the electron transfer reaction.