Large Substituent Effect on the Photochemical Rearrangement of 1,6-(N-Aryl)aza-[60]fulleroids to 1,2-(N-Arylaziridino)-[60]fullerenes

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• 作者：Akihiko Ouchi ; Ryota Hatsuda ; Bahlul Z. S. Awen ; Masako Sakuragi ; Reiko Ogura ; Tadahiro Ishii ; Yasuyuki Araki ; and Osamu Ito
• 刊名：Journal of the American Chemical Society
• 出版年：2002
• 出版时间：November 13, 2002
• 年：2002
• 卷：124
• 期：45
• 页码：13364 - 13365
• 全文大小：70K
• 年卷期：v.124,no.45(November 13, 2002)
• ISSN：1520-5126

文摘

Large substituent effects were observed in the rates and reaction mechanisms of the photochemical rearrangement of N-arylaza-[60]fulleroid 1 to N-arylaziridino-[60]fullerene 2, in which the difference of the rates between the fastest and the slowest (>2160-fold) was attained only by changing the aryl group from 1-naphthyl to 2-naphthyl. The decreasing order of the reaction rates in relation to the substituents was 1-naphthyl (1b) > 1-pyrenyl (1d) > phenyl (1a) > 2-naphthyl (1c). The reactions proceeded via triplet states of the fulleroids and a triplet sensitization of the reaction by rearranged product 2b was observed in the case of 1b. The slow reactions of 1a,c were interpretated by the participation of charge-separated species in the excited triplet states, which was supported by nanosecond transient absorption spectra.