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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Role of Polar Protic Solvents in the Dissociation and Reactivity of Photogenerated Radical Ion Pairs
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Role of Polar Protic Solvents in the Dissociation and Reactivity of Photogenerated Radical Ion Pairs

机译:极性质子溶剂在光生自由基离子对解离和反应性中的作用

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摘要

The UV photolysis of bimolecular charge transfer complexes is employed to yield reactive radical ions in their solvent-equilibrated electronic ground state. In polar protic media, noncovalent complexes of 1,2,4,5-tetracyanobenzene and toluene undergo efficient, ultrafast dissociation to ion pairs and equilibrate with their solvent environment before the resulting radical ions engage in electron transfer and proton abstraction on subnanosecond time scales. Solvent molecules play a critical role in these reactive pathways and in the dissociation and relaxation processes that precede them. We report a clear separation of time scales for these relaxation and reactive processes, which implies that solvent-solute interactions can be used as a tool for tuning the reaction pathways of equilibrated radical ions in solution.
机译:双分子电荷转移复合物的UV光解用于在其溶剂平衡的电子地位中产生反应性自由基离子。 在极性质子介质中,1,2,4,5-四环苯和甲苯的非共价络合物经历高效,超速解离与离子对,并且在所得到的自由基离子接合电子转移和亚亚倍的时间尺度上的质子抽象之前与其溶剂环境平衡。 溶剂分子在这些反应性途径和在它们之前的解离和放松过程中起着关键作用。 我们报告了这些弛豫和反应过程的清晰分离,这意味着溶剂溶质相互作用可用作调节溶液中平衡的自由基离子的反应途径的工具。

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