Large substituent effect on the photochemical rearrangement of 1,6-(N-Aryl)aza-[60]fulleroids to 1,2-(N-Arylaziridino)-[60]fullerenes.
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.
Ouchi
Akihiko
A
Research Institute for Green Technology, National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8565, Japan. ouchi.akihiko@aist.go.jp
Hatsuda
Ryota
R
Awen
Bahlul Z S
BZ
Sakuragi
Masako
M
Ogura
Reiko
R
Ishii
Tadahiro
T
Araki
Yasuyuki
Y
Ito
Osamu
O