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在光致电子转移过程中,树枝状分子对芪核心自由基阳离子形成和衰变的抑制作用。

Inhibition of the formation and decay of stilbene core radical cations by the dendron during the photoinduced electron transfer.

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 Phys Chem B. 2005 Jan 20;109(2):973-6. doi: 10.1021/jp045777j.

Abstract

Formation and decay processes of stilbene core radical cation (ST*+) during the photoinduced electron transfer have been studied for a series of stilbene bearing benzyl ether-type dendrons (D). ST*+ and the radical cation of peripheral dendron (D*+) were generated by intermolecular hole transfer from biphenyl radical cation, which was generated from photoinduced electron transfer from biphenyl to the singlet-excited 9,10-dicyanoanthracene in a mixture of acetonitrile and 1,2-dichloroethane (3:1). An intramolecular dimer radical cation of benzyl groups at the terminal of stilbene dendrimer was indicated as a hole trapping site. Subsequent hole transfer from the trapping site to the core ST generated ST*+. The shielding effects of D depending on the dendrimer generation on the growth and decay of ST*+ were observed. It was revealed for the first time that D acts as the hole trapping site and the hole conductor on the way of the exothermic hole transfer from the terminal of D to the central core ST. We also found that D inhibits the charge recombination with 9,10-dicyanoanthracene radical anion because of the steric hindrance.

摘要

在光诱导电子转移过程中,对一系列带有苄基醚型树枝状分子(D)的芪的芪核心自由基阳离子(ST*+)的形成和衰变过程进行了研究。ST*+和外围树枝状分子的自由基阳离子(D*+)是通过分子间空穴转移从联苯自由基阳离子产生的,联苯自由基阳离子是由联苯向乙腈和1,2 - 二氯乙烷(3:1)混合物中的单线态激发9,10 - 二氰基蒽进行光诱导电子转移产生的。芪树枝状大分子末端苄基的分子内二聚体自由基阳离子被表明为空穴捕获位点。随后空穴从捕获位点转移到核心ST产生了ST*+。观察到树枝状分子代数不同时,D对ST*+的增长和衰变的屏蔽效应。首次揭示了在从D的末端到中心核心ST的放热空穴转移过程中,D充当空穴捕获位点和空穴导体。我们还发现,由于空间位阻,D抑制了与9,10 - 二氰基蒽自由基阴离子的电荷复合。

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