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首页> 外文期刊>Chemistry: A European journal >Driving Force Dependence of Intermolecular Electron-Transfer Reactions of Fullerenes
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Driving Force Dependence of Intermolecular Electron-Transfer Reactions of Fullerenes

机译：富勒烯分子间电子转移反应的驱动力依赖性

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摘要

Pulse-radiolytic studies were performed to determine the rate constants of intermolecular electron transfer (k_et) from fullerenes (C_60, C_76, and C_78) to a series of arene radical cations in dichloromethane. The one-electron oxidation potentials of the employed arenes-corresponding to the one-electron reduction potentials of arene pi-radical cations-were detremined in dichloromethane to evaluate the driving forces of electron-transfer oxidation of fullerenes with arene pi-radical cations. The driving force dependence of log k_et shows a pronounced decrease towards the highly exothermic region, representing the first definitive confirmation of the existence of the Marcus inverted region in a truly intermolecular electron transfer. Electron-transfer reduction of fullerenes with anthracene radical anion was also examined by laser flash photolysis in benzonitrile. The anthracene radical anion was produced by photoinduced electron transfer from 10,10'-dimethyl-9,0',10,10'-tetrahydro-9,9'-biacridine [(AcrH)_2] to the singlet excited state of anthracene in benzonitrile. The raet constants of electron transfer (k_et) from anthracene radical anion to C_60, C_70, and C_60 derivative were determined from the decay of anthracene radical anion in the presence of various concentrations of the fullerene. Importantly, a significant decrease in the k_et value was observed at large driving forces (1.50 eV) as compared to the diffusion-limited value seen at smaller driving forces (0.96 eV). In conclusion, our study presents clear evidence for the Marcus inverted region in both the electron-transfer reduction and oxidation of fullerenes.
机译：进行了脉冲辐射分解研究，以确定从富勒烯（C_60，C_76和C_78）到二氯甲烷中一系列芳烃自由基阳离子的分子间电子转移（k_et）的速率常数。在二氯甲烷中测定所用芳烃的一电子氧化电位（对应于芳烃π-自由基阳离子的单电子还原电位），以评估芳烃与芳烃π-自由基阳离子进行电子转移氧化的驱动力。 log k_et的驱动力依赖性显示出朝着高放热区域的明显降低，这是对真正的分子间电子转移中Marcus反向区域的存在的首次确定确认。还通过在苯甲腈中的激光闪光光解检查了蒽自由基阴离子对富勒烯的电子转移还原。蒽自由基阴离子是由光诱导的电子从10,10'-二甲基-9,0'，10,10'-四氢-9,9'-二idine啶[（AcrH）_2]转移到蒽的单重激发态而产生的。苄腈。从蒽自由基阴离子在各种浓度的富勒烯存在下的衰变来确定从蒽自由基阴离子到C_60，C_70和C_60衍生物的电子转移（k_et）的Raet常数。重要的是，与较小驱动力（0.96 eV）的扩散极限值相比，在较大驱动力（1.50 eV）处的k_et值显着下降。总之，我们的研究为富勒烯的电子转移还原和氧化提供了马库斯倒置区域的明确证据。

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