超快激光光谱学
光化学
轨道能级差
分子内力
电子供体
接受者
化学
电子转移
吸收光谱法
吸收(声学)
激发态
光激发
酞菁
电子受体
单重态
材料科学
化学物理
光谱学
原子物理学
分子
有机化学
量子力学
物理
复合材料
催化作用
凝聚态物理
作者
Nathalie Zink‐Lorre,Enrique Font‐Sanchis,Sairaman Seetharaman,Paul A. Karr,Ángela Sastre‐Santos,Francis D’Souza,Fernando Fernández‐Lázaro
标识
DOI:10.1002/chem.201900973
摘要
Abstract Directly linked to promote strong intramolecular interactions, donor–acceptor dyads and a donor–acceptor–donor triad featuring zinc phthalocyanine (ZnPc) as electron donor and perylenediimide (PDI) as electron acceptor have been synthesized and characterized. Owing to complementary absorption features of the entities, improved light absorption was witnessed in these conjugates. The optimized geometry and electronic structures showed the majority of the highest occupied molecular orbital (HOMO) on the ZnPc entity, whereas the lowest unoccupied molecular orbital (LUMO) was on the PDI entity, suggesting that the charge‐separated states would be ZnPc + –PDI . − . The electrochemical and free‐energy calculations suggested exothermic energy and/or electron transfer processes via the singlet states of PDI or ZnPc entities depending on the excitation wavelength of the laser used. The measured rates using femtosecond pump‐probe spectroscopy coupled with global analysis of transient data revealed ultrafast energy transfer from 1 PDI* to ZnPc followed by charge separation. However, when ZnPc was selectively excited, only electron transfer was witnessed wherein the time constants for forward and reverse electron transfer processes followed Marcus predictions. The absorption in a wide section of the solar spectrum and the ultrafast charge separation suggest the usefulness of these systems as good photosynthetic models.
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