31.Light harvesting gold porphyrin - zinc phthalocyanine supramolecular donor-acceptor dyad
31.Light harvesting gold porphyrin - zinc phthalocyanine supramolecular donor-acceptor dyad
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31.光捕获金卟啉-锌酞菁超分子供体-受体二联体
DOI：
10.1039/c6pp00228e
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
E. El-Khouly and Shunichi Fukuzumi
中科院分区：
文献类型：
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作者：
Takashi Yanagishita;Toshiaki Kondo;and Hideki Masuda;E. El-Khouly and Shunichi Fukuzumi
本文报道了以金卟啉（AuPpy）为电子受体，酞菁锌（ZnPc）为电子供体组成的光捕获超分子二元体的光谱、电化学和激光光解研究，以模拟光合系统中的反应中心。为此，金卟啉被吡啶单元功能化，与酞菁锌轴向配位形成稳定的超分子AuPpy:ZnPc，反应速率为2.94 × 104M−1。稳态荧光测量显示，加入AuPpy后，单线态激发的ZnPc发射明显猝灭，表明电子从单线态激发的ZnPc转移到AuPpy。利用飞秒激光光解技术重新记录了酞菁锌自由基阳离子在近红外区的特征吸收带，证实了电子转移特性。研究发现，AuPpy:ZnPc超分子二元体表现出相对长寿命的自由基离子对，并在很宽的太阳光谱范围内吸收光，这表明它可能是一个有用的光合反应中心。
We reported herein the spectroscopic, electrochemical and laser photolysis studies for the newly constructed light harvesting supramolecular dyad composed of gold porphyrin (AuPpy), as an electron acceptor, and zinc phthalocyanine (ZnPc), as an electron donor, to mimic the reaction centre in the photosynthetic system. For this, gold porphyrin has been functionalized by pyridine units, which axially coordinated with zinc phthalocyanine to form the stable supramolecular AuPpy:ZnPc with a rate of 2.94 × 104M−1. Steady-state fluorescence measurements showed significant quenching of the singlet excited ZnPc emission with addition of AuPpy, suggesting an electron transfer from the singlet excited ZnPc to AuPpy. The electron transfer character was confirmed by recoding the characteristic absorption band of the zinc phthalocyanine radical cation in the NIR region by a femtosecond laser photolysis technique. The findings that the AuPpy:ZnPc supramolecular dyad exhibits relatively long-lived radical-ion pairs and absorbs light in a wide range of the solar spectrum suggest that it would be useful as a photosynthetic reaction centre.