Orientation effect of enhanced intersystem crossing in copper(II) porphyrin-free base porphyrin dimers

被引：18

作者：

Asano-Someda, M ^{[1
]}

Jinmon, A ^{[1
]}

Toyama, N ^{[1
]}

Kaizu, Y ^{[1
]}

机构：

[1] Tokyo Inst Technol, Dept Chem, Meguro Ku, Tokyo 1528551, Japan

来源：

INORGANICA CHIMICA ACTA | 2001年 / 324卷 / 1-2期

基金：

日本学术振兴会;

关键词：

orientation effect; copper(II) porphyrin-free base; porphyrin dimers;

D O I：

10.1016/S0020-1693(01)00539-4

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Intersystem crossing (ISC) enhanced by a remote unpaired electron through long-range interaction was studied in linear-type copper(II) porphyrin-free base porphyrin dimers in comparison with the gable-type dimers. The excited singlet state of the free base moiety is deactivated to its triplet manifolds quickly due to exchange interaction between the free base TC-electrons and copper unpaired d electron. While the ISC rates in the gable dimers show a simple relation with number of bonds of the linkage, two linear-type dimers behave differently. In the case of a p-phenyl bridged dimer, where the two porphyrin halves are almost parallel, the ISC rate is much larger than that expected from the simple through-bond coupling, which is applicable to the gable-type dimers. On the other hand, p-biphenyl bridged dimer, in which two halves are not parallel, does not show such an effect. Parallel orientation of the two terminals can play an important role in the long-range exchange coupling. (C) 2001 Elsevier Science B.V. All rights reserved.

引用

页码：347 / 351

页数：5

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