Remote Control on the Photochemical Rearrangement of 1,6-(N-Aryl)aza-[60]fulleroids to 1,2-(N-Arylaziridino)-[60]fullerenes by N-Substituted Aryl Groups
Remote Control on the Photochemical Rearrangement of 1,6-(N-Aryl)aza-[60]fulleroids to 1,2-(N-Arylaziridino)-[60]fullerenes by N-Substituted Aryl Groups
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N-取代芳基对 1,6-(N-芳基)氮杂-[60]富勒烯光化学重排至 1,2-(N-芳基氮丙啶基)-[60]富勒烯的远程控制
DOI：
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发表时间：
2004
期刊：
影响因子：
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通讯作者：
O. Ito
中科院分区：
文献类型：
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作者：
A. Ouchi;B. Z. Awen;R. Hatsuda;Reiko Ogura;T. Ishii;Y. Araki;O. Ito
1，6-(N-芳基)氮杂-[60]富勒烷(1)的光化学重排为1，2-(N-芳氮基)-[60]富勒烯(2)依赖于远离反应中心的N-芳基取代基。对N-取代基的系统动力学研究表明，光化学重排反应速率的顺序为1-萘基(1b)&1-吡喃基(1d)>；苯基(1a)>；2-萘基(1c)。反应速率变化约2200倍的大取代基效应可用反应机理的变化来解释。衍生物1b、d的快速光化学重排通过正常的三重态1进行；在1b的情况下，产物2b的三重态敏化也起作用。对于低重排速率的1a，c，纳秒瞬时吸收光谱显示不同的三重态参与，即N-芳基取代基和富勒烯之间的电子转移。
Photochemical rearrangement of 1,6-(N-aryl)aza-[60]fulleroids (1) to 1,2-(N-arylaziridino)-[60]fullerenes (2) depends on the N-aryl substituents remote from the reaction center. A systematic kinetic study of the N-substituents discloses a decrease in the reaction rates of the photochemical rearrangement in the order 1-naphthyl (1b) > 1-pyrenyl (1d) > phenyl (1a) > 2-naphthyl (1c). The large substituent effect in the rates, which vary by ca. 2200-fold, is interpreted in terms of changes in the reaction mechanisms. The fast photochemical rearrangement of derivatives 1b,d proceeds through the normal triplet states of 1; in the case of 1b, triplet sensitization by the product 2b also operates. For the slow rearrangement rates of 1a,c, nanosecond transient absorption spectroscopy reveals that different triplet states participate, namely, electron transfer between the N-aryl substituent and the fullerene.