Enhanced intersystem crossing due to long-range exchange interaction in copper(II) porphyrin-free base porphyrin dimers: HOMO and spacer dependence

被引：14

作者：

Asano, Motoko S. ^{[1
]}

Okamura, Kazuma ^{[2
]}

Jin-mon, Akihoro ^{[2
]}

Takahashi, Sadaharu ^{[2
]}

Kaizu, Youkoh ^{[2
]}

机构：

[1] Tokyo Metropolitan Univ, Dept Chem, Hachioji, Tokyo 1920397, Japan

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

来源：

CHEMICAL PHYSICS | 2013年 / 419卷

关键词：

Photoexcited state; Unpaired electron; Long-range coupling; Superexchange; Fluorescence; INTRAMOLECULAR ENERGY-TRANSFER; COVALENTLY-LINKED PORPHYRIN; PHOTOINDUCED ELECTRON-TRANSFER; CHARGE-TRANSFER; PHOTOSYNTHETIC ANTENNA; TEMPERATURE-DEPENDENCE; MULTIPORPHYRIN ARRAYS; SPIN POLARIZATION; STATE; COMMUNICATION;

D O I：

10.1016/j.chemphys.2013.03.010

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Photodynamics induced by long-range exchange interaction was studied in two series of copper(II) porphyrin - free base porphyrin dimers linked via an aromatic spacer: one has a(2u) orbital as HOMO in the porphyrin pi-system and the other has a(1u) orbital. Dependence on the HOMO as well as that on the spacer is presented for enhanced intersystem crossing (EISC) occurring in the free base half due to long-range coupling with the copper unpaired electron. Semilogarithmic plots of EISC rates vs. number of bonds show a linear correlation in each series of dimers. It was found that the two correlation lines show the same slope but different intercepts. This clearly indicates that electronic communication within the linkage does not depend on the terminal chromophore, while the terminal pi-system affects the magnitude of EISC rates. Separately, a general expression for EISC rate, involving coupling between the terminal and linkage, was derived theoretically. (C) 2013 Elsevier B. V. All rights reserved.

引用

页码：250 / 260

页数：11

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