Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 120-749, Korea.
Chem Soc Rev. 2012 Jul 21;41(14):4808-26. doi: 10.1039/c2cs35022j. Epub 2012 Jun 1.
Since highly symmetric cyclic architecture of light-harvesting antenna complex LH2 in purple bacteria was revealed in 1995, there has been a renaissance in developing cyclic porphyrin arrays to duplicate natural systems in terms of high efficiency, in particular, in transferring excitation energy. This tutorial review highlights the mechanisms and rates of excitation energy transfer (EET) in a variety of synthetic cyclic porphyrin arrays on the basis of time-resolved spectroscopic measurements performed at both ensemble and single-molecule levels. Subtle change in structural parameters such as connectivity, distance, and orientation between neighboring porphyrin moieties exquisitely modulates not only the nature of interchromophoric interactions but also the rates and efficiencies of EET. The relationship between the structure and EET dynamics described here should assist a rational design of novel cyclic porphyrin arrays, more contiguous to real applications in artificial photosynthesis.
自 1995 年发现紫色细菌中光捕获天线复合物 LH2 的高度对称环状结构以来，人们一直在复兴开发环状卟啉阵列，以在高效率方面复制自然系统，特别是在传递激发能量方面。本综述强调了基于在集体和单分子水平上进行的时间分辨光谱测量，在各种合成环状卟啉阵列中激发能量转移（EET）的机制和速率。结构参数（如连接性、距离和相邻卟啉部分之间的取向）的微小变化不仅精巧地调节了发色团之间的相互作用的性质，而且还调节了 EET 的速率和效率。这里描述的结构与 EET 动力学之间的关系应该有助于合理设计新型环状卟啉阵列，使其更接近人工光合作用中实际应用的连续性。
