Photoinduced electron transfer from excited [tris(2,2'-bipyridine)ruthenium(II)]~(2+) to a series of anthraquinones with small positive or negative Gibbs energy of reaction. Marcus behavior and negative activation enthalpies

Rudolf Frank; Gerhard Greiner; Hermann Rau

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Photoinduced electron transfer from excited [tris(2,2'-bipyridine)ruthenium(II)]~(2+) to a series of anthraquinones with small positive or negative Gibbs energy of reaction. Marcus behavior and negative activation enthalpies

机译：光激发电子从激发的[tris（2,2'-联吡啶）钌（II）]〜（2+）转移到一系列具有较小正或负吉布斯反应能的蒽醌。马库斯行为和负激活焓

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In the electron transfer (ET) quenching reactions of electronically excited ~*Ru(byp)_3~(2+) in acetonitrile an increase of the rate constant k_q is observed in the series of 2-methyl-, 1-chloro-, and 1-nitro-anthraquinone as quenchers. If alkali salts are used as supporting electrolytes the AQ~(.-) radical anions are found to form specific associates with the alkali cations. In the presence of non-associating tetraalkylammonium salts the system follows the predictions of Marcus theory. Numerical methods are developed which allow the determination of the rate constants of the conventional reaction scheme. This analysis shows that the quantum yield of free AQ~(.-) radical anion formation is governed by the interplay of forward, reverse and back ET. Negative activation enthalpies are found for the activation controlled quenching reactions. From the numerical analysis of the system of rate constants it is inferred that this phenomenon is due to the elementary ET step in the reaction sequence. We discuss the pre-equilibrium and elementary reaction models for reactions with negative activation enthalpy and present, to our knowledge, the first example of successful discrimination between them.

机译：在乙腈中电子激发的〜* Ru（byp）_3〜（2+）的电子转移（ET）猝灭反应中，观察到速率常数k_q在2-甲基，1-氯和1-硝基蒽醌作为淬灭剂。如果将碱金属盐用作支持电解质，则会发现AQ〜（.-）自由基阴离子与碱金属阳离子形成特定的缔合体。在非缔合四烷基铵盐的存在下，该系统遵循马库斯理论的预测。开发了数值方法，其允许确定常规反应方案的速率常数。分析表明，游离AQ〜（.-）自由基阴离子形成的量子产率受正向，反向和反向ET相互作用的支配。对于活化控制的猝灭反应，发现了负的活化焓。从速率常数系统的数值分析可以推断出，这种现象是由于反应序列中的基本ET步骤引起的。我们讨论了具有负激活焓的反应的平衡前和基本反应模型，并据我们所知提供了成功区分它们之间的第一个例子。

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《Physical chemistry chemical physics: PCCP》 |1999年第15期|共10页
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Rudolf Frank; Gerhard Greiner; Hermann Rau;
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中图分类物理化学（理论化学）、化学物理学;物理学;
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1. Photoinduced electron transfer from excited [tris(2,2'-bipyridine)ruthenium(II)]~(2+) to a series of anthraquinones with small positive or negative Gibbs energy of reaction. Marcus behavior and negative activation enthalpies [J] . Rudolf Frank, Gerhard Greiner, Hermann Rau Physical chemistry chemical physics: PCCP . 1999,第15期

机译：光激发电子从激发的[tris（2,2'-联吡啶）钌（II）]〜（2+）转移到一系列具有较小正或负吉布斯反应能的蒽醌。马库斯行为和负激活焓
2. Effects of DNA on driving force dependence of photoinduced electron transfer from the excited state of tris(2,2-bipyridine)ruthenium(II) to intercalators in DNA Distinction between intra- and inter-DNA pathways [J] . Shunichi Fukuzumi, Makiko Tanaka, Mari Nishimine, Journal of Photochemistry and Photobiology, A. Chemistry . 2005,第2a3期

机译：DNA对内部和内部DNA途径之间的DNA区分的光诱导电子从三（2,2-联吡啶）钌（II）的激发态到嵌入剂的驱动力依赖性的影响
3. Photoinduced Electron Transfer in a Tris(2,2'-bipyridine)-C_(60)-ruthenium(II) Dyad: Evidence of Charge Recombination to a Fullerene Excited State [J] . Antonin Vlcek Jr. Chemtracts . 1999,第8期

机译：Tris（2,2'-联吡啶）-C_（60）-钌（II）Dyad中的光诱导电子转移：电荷复合到富勒烯激发态的证据。
4. I. Ground-state association between phenothiazine and tris(diimine)ruthenium(II) complexes: Its role in highly efficient photoinduced charge separation. II. Ligand modifications of cobalt complexes to increase efficiency of electron-transfer mediators in dye-sensitized solar cells [D] . Weber, John 2012

机译：一，吩噻嗪与三（二亚胺）钌（II）配合物之间的基态缔合：在高效光诱导电荷分离中的作用。二。钴配合物的配体修饰，以提高染料敏化太阳能电池中电子转移介体的效率
5. Light-Activated Protein Inhibition through Photoinduced Electron Transfer of a Ruthenium(II)–Cobalt(III) Bimetallic Complex [O] . Robert J. Holbrook, David J. Weinberg, Mark D. Peterson, -1

机译：通过光诱导电子转移钌（II）-钴（III）双金属配合物来抑制光激活的蛋白质
6. Electron-transfer Reaction from Sodium Benzenethiolate to Acceptors Assisted by Photo-excited Tris(2,2′-bipyridine)ruthenium(II) [O] . Tokuji Miyashita, Minoru Matsuda 1981

机译：来自苯并乙烯钠钠的电子转移反应对受照片激发三（2,2'-硼丙啶）钌（II）的辅助反应
7. Electron Transfer Quenching of the Luminescent Excited State of Tris(2,2'-Bipyridine)Ruthenium (II). A Flash Photolysis Relaxation Technique for Measuring the Rates of Very Rapid Electron Transfer Reactions. [R] . Bock, C. R., Meyer, T. J., Whitten, D. G. 1974

机译：三（2,2'-联吡啶）钌（II）发光激发态的电子转移猝灭。闪光光解弛豫技术测量快速电子转移反应速率。

Photoinduced electron transfer from excited [tris(2,2'-bipyridine)ruthenium(II)]~(2+) to a series of anthraquinones with small positive or negative Gibbs energy of reaction. Marcus behavior and negative activation enthalpies

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