Cyclic Tetramers of ZincChlorophylls as a Coupled Light-Harvesting Antenna-Charge Separation System
Cyclic Tetramers of ZincChlorophylls as a Coupled Light-Harvesting Antenna-Charge Separation System
复制标题
叶绿素锌的环状四聚体作为耦合光捕获天线电荷分离系统
DOI：
10.1002/chem.201503789
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
Joe Otsuki
中科院分区：
文献类型：
--
作者：
Yoshinao Shinozaki;Kei Ohkubo;Shunichi Fukuzumi;Kosuke Sugawa ;Joe Otsuki
报道了一种耦合的捕光天线-电荷分离系统，该系统由自组装的锌叶绿素衍生物组成，该衍生物包含电子接受单元。通过吡啶附加的锌叶绿素衍生物ZnPy和进一步用富勒烯单元ZnPyC 60修饰的锌叶绿素衍生物的共组装来构建并入电子受体的环状四聚体。对ZnPyC 60和ZnPyC 60的单独四聚体以及它们的共四聚体进行了全面的稳态和时间分辨光谱研究。组装内单重态能量转移通过ZnPy四聚体中的单重态-单重态湮灭来证实。电子从单线态二氢卟酚单元转移到富勒烯单元的过程可以通过富勒烯自由基阴离子在ZnPyC 60四聚体中的瞬时吸收来清楚地证明。最后，利用共四聚体，展示了具有几乎100%量子效率的耦合的光捕获和电荷分离系统。
A coupled light‐harvesting antenna–charge‐separation system, consisting of self‐assembled zinc chlorophyll derivatives that incorporate an electron‐accepting unit, is reported. The cyclic tetramers that incorporated an electron acceptor were constructed by the co‐assembly of a pyridine‐appended zinc chlorophyll derivative,ZnPy, and a zinc chlorophyll derivative further decorated with a fullerene unit,ZnPyC60. Comprehensive steady‐state and time‐resolved spectroscopic studies were conducted for the individual tetramers ofZnPyandZnPyC60as well as their co‐tetramers. Intra‐assembly singlet energy transfer was confirmed by singlet–singlet annihilation in theZnPytetramer. Electron transfer from the singlet chlorin unit to the fullerene unit was clearly demonstrated by the transient absorption of the fullerene radical anion in theZnPyC60tetramer. Finally, with the co‐tetramer, a coupled light‐harvesting and charge‐separation system with practically 100 % quantum efficiency was demonstrated.