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苄基醚型树枝状分子作为空穴捕获天线的作用,以及在具有芪核心和苄基醚型树枝状分子的芪树枝状大分子双光子电离过程中,用于用氯离子中和芪核心自由基阳离子的屏蔽作用。

Effects of benzyl ether type dendrons as hole-harvesting antennas, and shielding for the neutralization of stilbene core radical cations with chloride ion during two-photon ionization of stilbene dendrimers having stilbene core and benzyl ether type dendrons.

作者信息

Hara Michihiro, Samori Shingo, Cai Xichen, Tojo Sachiko, Arai Tatsuo, Momotake Atsuya, Hayakawa Junpei, Uda Mayuko, Kawai Kiyohiko, Endo Masayuki, Fujitsuka Mamoru, Majima Tetsuro

机构信息

The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.

出版信息

J Am Chem Soc. 2004 Nov 3;126(43):14217-23. doi: 10.1021/ja046650a.

Abstract

The two-photon ionization (TPI) process (308 and 266 nm) of stilbene dendrimers having a stilbene core and benzyl ether type dendrons has been investigated in an acetonitrile and 1,2-dichloroethane mixture (3:1) in order to elucidate the dendrimer effects. The quantum yield of the formation of stilbene core radical cation during the 308-nm TPI was independent of the dendron generation of the dendrimers, whereas a generation dependence of the quantum yield of the radical cation was observed during the 266-nm TPI, where both the stilbene core and benzyl ether type dendron were ionized, suggesting that the subsequent hole transfer occurs from the dendron to the stilbene core, and that the dendron acts as a hole-harvesting antenna. The neutralization rate of the stilbene core radical cation with the chloride ion, generated from the dissociative electron capture by 1,2-dichloroethane, decreased with the increase in the dendrimer generation, suggesting that the dendron is an effective shield of the stilbene core radical cation against the chloride ion.

摘要

为了阐明树枝状聚合物效应,研究了具有芪核心和苄基醚型树枝单元的芪树枝状聚合物在乙腈和1,2 - 二氯乙烷混合物(3:1)中的双光子电离(TPI)过程(308和266 nm)。在308 nm TPI过程中,芪核心自由基阳离子形成的量子产率与树枝状聚合物的树枝单元代数无关,而在266 nm TPI过程中观察到自由基阳离子量子产率的代数依赖性,此时芪核心和苄基醚型树枝单元均被电离,这表明随后的空穴转移从树枝单元发生到芪核心,并且树枝单元起到空穴捕获天线的作用。由1,2 - 二氯乙烷的解离电子俘获产生的氯离子与芪核心自由基阳离子的中和速率随着树枝状聚合物代数的增加而降低,这表明树枝单元是芪核心自由基阳离子对抗氯离子的有效屏蔽。

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