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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photoinduced Electron Transfer from N,N-Dimethylaniline to Pyrrolidinofullerenes (C+(60)(C_3H_6N)R): Emphasized Substituent Effects with Solvent Polarity Change
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Photoinduced Electron Transfer from N,N-Dimethylaniline to Pyrrolidinofullerenes (C+(60)(C_3H_6N)R): Emphasized Substituent Effects with Solvent Polarity Change

机译：从N，N-二甲基苯胺到吡咯烷基富勒烯（C +（60）（C_3H_6N）R）的光诱导电子转移：带有溶剂极性变化的取代基效应

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摘要

Photoinduced electron-transfer reactions of pyrrolidinofullerenes {C_(60)(C_3H_6N)R; R = H (1), C_6H-4NO_2-p (2), C_6H_4CHO-p (3), C_6H_5 (4), C_6H_4OMe-p (5), and C_6H_4NMe_2-p (6)} with N,N-dimethylaniline have been systematically studied by means of nanosecond laser photolysis. From the direct observation of the rises of the anion radicals accompanied by the decays of the triplet states of the fullerenes, the rate constants of electron-transfer reactions (k_(ET)) via the triplet states were evaluated in polar solvents. Although the k_(ET) values are considerably decreased by the substituents as compared with that of pristine C_(60), the electron is accepted by the C_(60) moiety. Among the derivatives, the k_(ET) values of 2 and 3 with electron-withdrawing groups are larger than those of 4 and 1. In less polar solvent, such a substituent effect becomes prominent with decrease in the k_(ET) values, which is in accord with the reactivity-selectivity principle. This behavior can be explained by the Rehm-Weller relation and/or Marcus equation in consideration of the solvent polarity change. Back-electron-transfer rate constants in less polar solvent are larger than those in polar solvent, which is related to the desolvation process and/or loose ion pair formation.
机译：吡咯烷基富勒烯{C_（60）（C_3H_6N）R;的光诱导电子转移反应; R = H（1），C_6H-4NO_2-p（2），C_6H_4CHO-p（3），C_6H_5（4），C_6H_4OMe-p（5）和具有N，N-二甲基苯胺的C_6H_4NMe_2-p（6）}通过纳秒激光光解的方法进行了系统研究。从直接观察到的阴离子自由基的上升伴随着富勒烯的三重态的衰变，在极性溶剂中评估了通过三重态的电子转移反应的速率常数（k_（ET））。尽管与原始C_（60）相比，取代基使k_（ET）值大大降低，但电子被C_（60）部分接受。在这些衍生物中，具有吸电子基团的2和3的k_（ET）值大于4和1的k_（ET）值。在极性较小的溶剂中，随着k_（ET）值的降低，这种取代作用变得明显。符合反应选择性原则。可以通过考虑溶剂极性变化的Rehm-Weller关系和/或Marcus方程来解释这种行为。极性较小的溶剂中的反向电子传输速率常数大于极性溶剂中的反向电子传输速率常数，这与去溶剂化过程和/或疏松的离子对形成有关。

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