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Role of the Special Pair in the Charge-Separating Event in Photosynthesis

机译:特殊对在光合作用中电荷分离事件中的作用

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We synthesized special-pair/ electron-acceptor systems consisting of a complementary slipped cofacial dimer of imidazolyl-substituted zinc porphyrin,bearing pyromellitdiimide as the electron acceptor.In the case of the dimer,the first and second oxidation potentials were split into a total of four peaks in the differential pulse vol-tammetry measurement.Furthermore,the shift values of the first oxidation potentials obtained by changing the solvent polarity for the dimer were almost half of those observed for the monomer.These results indicate that the radical cation is delocalized over the whole n system of the dimer.Time-resolved transient absorption measurements revealed that,relative to the cor-responding monomer,the dimer accelerated the charge separation rate,but decelerated the charge recombination rate.The smaller reorganization energy of the slipped cofacial dimer relative to that of the monomeric system demonstrates the significance of the special-pair arrangement for efficient charge separation in photosynthesis.
机译:我们合成了特殊对/电子受体体系,该体系由咪唑基取代的卟啉锌互补的互补滑面二聚体组成,并以均苯四酸二亚胺为电子受体。在差分脉冲伏安法测量中有四个峰。此外,通过改变二聚体的溶剂极性获得的第一氧化电位的位移值几乎是单体观察到的一半。这些结果表明,自由基阳离子在时间分辨的瞬态吸收测量结果表明,相对于相应的单体,二聚体加快了电荷分离速率,但减慢了电荷复合速率。滑动面二聚体的相对重组能越小对单体系统的反应证明了特殊对安排对有效的意义t光合作用中的电荷分离。

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