Electron-Transfer Reactions Triggered by Uncharged or Cationic Photosensitizer: Methodology for Generation of o-Quinodimethane and Analysis of Back Electron-Transfer Process

被引：3

作者：

Matsui, Yasunori ^{[2
,3
]}

Ikeda, Teruyo ^{[4
]}

Takahashi, Yasutake ^{[5
]}

Kamata, Masaki ^{[6
]}

Akagi, Megumi ^{[4
]}

Ohya, Yukako ^{[4
]}

Fujino, Ryota ^{[6
]}

Namai, Hayato ^{[4
]}

Ohta, Eisuke ^{[2
,3
]}

Ogaki, Takuya ^{[2
,3
]}

Miyashi, Tsutomu ^{[4
]}

Tero-Kubota, Shozo ^{[7
]}

Mizuno, Kazuhiko ^{[2
]}

Ikeda, Hiroshi ^{[1
]}

机构：

[1] Osaka Prefecture Univ, Dept Appl Chem, Grad Sch Engn, Res Inst Mol Elect Devices, Sakai, Osaka 5998531, Japan

[2] Osaka Prefecture Univ, Dept Appl Chem, Grad Sch Engn, Sakai, Osaka 5998531, Japan

[3] Osaka Prefecture Univ, Res Inst Mol Elect Devices, Sakai, Osaka 5998531, Japan

[4] Tohoku Univ, Grad Sch Sci, Dept Chem, Sendai, Miyagi 9808578, Japan

[5] Univ Toyama, Div Chem, Grad Sch Med & Pharmaceut Sci, Toyama 9300194, Japan

[6] Niigata Univ, Fac Educ, Dept Chem, Niigata 9502181, Japan

[7] Tohoku Univ, Inst Multidisciplinary Res Adv Mat, Sendai, Miyagi 9808577, Japan

来源：

ASIAN JOURNAL OF ORGANIC CHEMISTRY | 2017年 / 6卷 / 04期

基金：

日本科学技术振兴机构;

关键词：

electron transfer; laser chemistry; luminescence; quinodimethanes; thermoluminescence; PHOTOSYNTHETIC REACTION-CENTER; RADICAL-CATION; FREE-ENERGY; PHOTOCHEMICAL-REACTIONS; TRIPHENYLPYRYLIUM SALT; AROMATIC-HYDROCARBONS; INVERTED REGION; XYLYLENE; MECHANISM; METHYLENECYCLOPROPANE;

D O I：

10.1002/ajoc.201600570

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Photoinduced electron transfer (PET) followed by back electron transfer (BET) reactions of 1,2-bis(-styryl)benzenes 1, generates o-quinodimethane derivative 2 via the corresponding radical cation 2(+). This process serves as a facile method to form o-quinodimethane intermediates. The intermediacy of 2(+) and 2 were confirmed by using various spectroscopic methods and trapping reactions with O-3(2) and dienophiles. Kinetic analysis using nanosecond time-resolved absorption showed that 2(+) was transformed to 2 via a BET process, in which the decay of 2(+) and rise of 2 have almost the same rate constants of k(DECAY)=5.6x10(5)s(-1) and k(RISE)=5.9x10(5)s(-1), respectively. The net BET rate constant evaluated by using Marcus theory is much faster than these experimental values, owing to the reduction based on diffusion.

引用

页码：458 / 468

页数：11