调节光合作用特殊对模型中的电子传递驱动力。

IF 3.9 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - A European Journal Pub Date : 2024-11-06 DOI:10.1002/chem.202402700

Ivana Ramírez-Wierzbicki, Luciano Sanchez Merlinsky, German E Pieslinger, Sofía Domínguez, Leonardo D Slep, Luis M Baraldo, Alejandro Cadranel

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引用次数: 0

摘要

通过可见光激发双金属钌多吡啶族，制备了作为光合反应中心模型的光诱导混合价（PI-MV）MLCT 状态，其分子式为[RuII(ttpy)(bpy)(𝜇-CN)RuII(py)4L]n+ (RuRuLn+)，其中 L = Cl-、NCS-、DMAP 和 ACN。超快瞬态吸收光谱可以监测 6000 至 11000 cm-1 之间的光诱导 IVCT 波段。DFT 和 (TD)DFT 计算得出的 Mulliken 自旋密度显示，电荷密度分布的变化取决于配体的取代模式。结果表明，PI-MV 系统的范围从非退化 II 类到退化 III 类，电子耦合在 1000 到 3500 cm-1 之间。这些发现为控制电荷转移/电荷分离激发态（如光合作用反应中心所涉及的激发态）中的电子定位-去定位提供了指导。

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Tuning Electron-Transfer Driving Force in Photosynthetic Special Pair Models.

Visible-light excitation of a family of bimetallic ruthenium polypyridines with the formula [Ru^II(tpy)(bpy)(-CN)Ru^II(py)₄L]ⁿ⁺ (RuRuLⁿ⁺), where L=Cl^-, NCS^-, DMAP and ACN, was used to prepare photoinduced mixed-valence (PI-MV) MLCT states as models of the photosynthetic reaction center. Ultrafast transient absorption spectroscopy allowed to monitor photoinduced IVCT bands between 6000 and 11000 cm^-1. Mulliken spin densities resulting from DFT and (TD)DFT computations revealed the modulation of the charge density distribution depending on the ligand substitution pattern. Results are consistent with PI-MV systems ranging from non-degenerate Class II to degenerate Class III or II/III, with electronic couplings between 1000 and 3500 cm^-1. These findings guide the control electron localization-delocalization in charge-transfer/charge-separated excited states, like those involved in the photosynthetic reaction center.

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来源期刊

Chemistry - A European Journal 化学-化学综合

CiteScore

7.90

自引率

4.70%

发文量

1808

审稿时长

1.8 months

期刊介绍： Chemistry—A European Journal is a truly international journal with top quality contributions (2018 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields. Based in Europe Chemistry—A European Journal provides an excellent platform for increasing the visibility of European chemistry as well as for featuring the best research from authors from around the world. All manuscripts are peer-reviewed, and electronic processing ensures accurate reproduction of text and data, plus short publication times. The Concepts section provides nonspecialist readers with a useful conceptual guide to unfamiliar areas and experts with new angles on familiar problems. Chemistry—A European Journal is published on behalf of ChemPubSoc Europe, a group of 16 national chemical societies from within Europe, and supported by the Asian Chemical Editorial Societies. The ChemPubSoc Europe family comprises: Angewandte Chemie, Chemistry—A European Journal, European Journal of Organic Chemistry, European Journal of Inorganic Chemistry, ChemPhysChem, ChemBioChem, ChemMedChem, ChemCatChem, ChemSusChem, ChemPlusChem, ChemElectroChem, and ChemistryOpen.