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光合特殊对模型中电子转移驱动力的调控

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

作者信息

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

机构信息

Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Química Inorgánica, Analítica y Química Física, Pabellón 2, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina.

CONICET - Universidad de Buenos Aires. Instituto de Química Física de Materiales, Medio Ambiente y Energía (INQUIMAE), Pabellón 2, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina.

出版信息

Chemistry. 2025 Jan 9;31(2):e202402700. doi: 10.1002/chem.202402700. Epub 2024 Nov 21.

DOI:10.1002/chem.202402700
PMID:39503741
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11724256/
Abstract

Visible-light excitation of a family of bimetallic ruthenium polypyridines with the formula [Ru(tpy)(bpy)(-CN)Ru(py)L] (RuRuL), 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. 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. These findings guide the control electron localization-delocalization in charge-transfer/charge-separated excited states, like those involved in the photosynthetic reaction center.

摘要

利用通式为[Ru(tpy)(bpy)(-CN)Ru(py)L]（RuRuL，其中L = Cl、NCS、DMAP和ACN）的一类双金属钌多吡啶配合物的可见光激发，制备光诱导混合价态（PI-MV）的MLCT态，作为光合反应中心的模型。超快瞬态吸收光谱法能够监测6000至11000 cm之间的光诱导IVCT带。由DFT和(TD)DFT计算得出的 Mulliken自旋密度揭示了电荷密度分布随配体取代模式的变化。结果与从非简并II类到简并III类或II/III类的PI-MV体系一致，其电子耦合在1000至3500 cm之间。这些发现为控制电荷转移/电荷分离激发态中的电子定域-离域提供了指导，光合反应中心中涉及的激发态即属此类。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/ab6b280c33e0/CHEM-31-e202402700-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/fb455ca676c1/CHEM-31-e202402700-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/084188b48755/CHEM-31-e202402700-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/893974c92ebb/CHEM-31-e202402700-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/626bb5d9e401/CHEM-31-e202402700-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/c54c44a84dcf/CHEM-31-e202402700-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/ab6b280c33e0/CHEM-31-e202402700-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/fb455ca676c1/CHEM-31-e202402700-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/084188b48755/CHEM-31-e202402700-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/893974c92ebb/CHEM-31-e202402700-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/626bb5d9e401/CHEM-31-e202402700-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/c54c44a84dcf/CHEM-31-e202402700-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f715/11724256/ab6b280c33e0/CHEM-31-e202402700-g005.jpg

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本文引用的文献

1
Photoinduced Intervalence Charge Transfers: Spectroscopic Tools to Study Fundamental Phenomena and Applications.光致间价电荷转移：研究基本现象和应用的光谱工具。
Chemphyschem. 2022 Oct 19;23(20):e202200384. doi: 10.1002/cphc.202200384. Epub 2022 Aug 3.
2
Bifurcation of excited state trajectories toward energy transfer or electron transfer directed by wave function symmetry.激发态轨迹根据波函数对称性分叉，分别指向能量转移或电子转移。
Proc Natl Acad Sci U S A. 2021 Jan 26;118(4). doi: 10.1073/pnas.2018521118.
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The Electron Transfer Process in Mixed Valence Compounds with a Low-lying Energy Bridge in Different Oxidation States.
具有处于不同氧化态的低能桥的混合价化合物中的电子转移过程。
Angew Chem Int Ed Engl. 2021 Feb 23;60(9):4804-4814. doi: 10.1002/anie.202014501. Epub 2021 Jan 15.
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Does geometry matter? Effect of the ligand position in bimetallic ruthenium polypyridine siblings.几何结构重要吗？双金属钌多吡啶类似物中配体位置的影响。
Dalton Trans. 2020 Apr 1;49(13):4125-4135. doi: 10.1039/d0dt00040j.
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A Hole Delocalization Strategy: Photoinduced Mixed-Valence MLCT States Featuring Extended Lifetimes.一种空穴离域策略：具有延长寿命的光致混合价态MLCT态
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Inversion of donor-acceptor roles in photoinduced intervalence charge transfers.光致价间电荷转移中给体-受体角色的反转
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Exploring the localized to delocalized transition in non-symmetric bimetallic ruthenium polypyridines.
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