Long-lived charge-separated states of simple electron donor-acceptor dyads using porphyrins and phthalocyanines
Long-lived charge-separated states of simple electron donor-acceptor dyads using porphyrins and phthalocyanines
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DOI：
10.1142/s1088424608000376
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发表时间：
2008-09
影响因子：
1.5
通讯作者：
K. Ohkubo;S. Fukuzumi
中科院分区：
文献类型：
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作者：
K. Ohkubo;S. Fukuzumi
电子转移过程的控制描述了一些含有卟啉或酞菁的电子供体-受体二元体作为光合反应中心的模型。二联体分子内电子转移速率受电子转移驱动力和电子转移重组能的控制。电子转移反应需要小的重组能和大的电荷重组驱动力才能形成长寿命的电荷分离态。特别是直接连接的氯锌-富勒烯二偶体，在-150℃下具有最长的120 s的电荷分离态寿命，比天然光合反应中心的寿命和能量都要长得多。另一方面，基于酞菁的供体-受体二偶体（酞菁硅-富勒烯和酞菁锌-苝酰亚胺）的电荷分离态是短暂的，因为电荷重组形成了发色团的低三重态激发态。e……
Control of electron-transfer processes is described for a number of electron donor-acceptor dyads containing porphyrins or phthalocyanines as models for the photosynthetic reaction center. The rates for intramolecular electron transfer in the dyads are controlled by the driving force and reorganization energy of electron transfer. The small reorganization energy of electron transfer reactions and large driving force of charge recombination are required to form long-lived charge-separated states. A directly linked zinc chlorin-fullerene dyad, especially, has the longest lifetime of charge-separated state at 120 s at -150 °C, which is a much longer lifetime and higher energy than those of natural photosynthetic reaction centers. On the other hand, the charge-separated states of the phthalocyanine-based donor-acceptor dyads (silicon phthalocyanine-fullerene, and zinc phthalocyanine-perylenebisimide) are short-lived since charge recombination forms the low-lying triplet excited state of the chromophore. The e...