Tuning Electron-Transfer Driving Force in Photosynthetic Special Pair Models

被引：1

作者：

Ramirez-Wierzbicki, Ivana ^{[1
,2
]}

Merlinsky, Luciano Sanchez ^{[1
,2
]}

Pieslinger, German E. ^{[1
,3
,4
]}

Dominguez, Sofia ^{[1
,2
]}

Slep, Leonardo D. ^{[1
,2
]}

Baraldo, Luis M. ^{[1
,2
]}

Cadranel, Alejandro ^{[1
,2
,5
,6
]}

机构：

[1] Univ Buenos Aires, Fac Ciencias Exactas & Nat, Dept Quim Inorgan Analit & Quim Fis, Pabellon 2,Ciudad Univ,C1428EHA, Buenos Aires, Argentina

[2] Univ Buenos Aires, CONICET, Inst Quim Fis Mat Medio Ambiente & Energia INQUIMA, Pabellon 2,Ciudad Univ,C1428EHA, Buenos Aires, Argentina

[3] Univ Buenos Aires, CONICET, Inst Quim & Fisicoquim Biol IQUIFIB, Junin 956,C1113AAD, Buenos Aires, Argentina

[4] Donostia Int Phys Ctr, Paseo Manuel Lardizabal 4, Donostia San Sebastian 20018, Spain

[5] Friedrich Alexander Univ Erlangen Nurnberg, Dept Chem & Pharm, Phys Chem, Egerlandstr 3, D-91058 Erlangen, Germany

[6] Friedrich Alexander Univ Erlangen Nurnberg FAU, Interdisciplinary Ctr Mol Mat, Egerlandstr 3, D-91058 Erlangen, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2025年 / 31卷 / 02期

关键词：

electron transfer; redox asymmetry; transient absorption; solar energy conversion; photosynthesis; TRANSITION-METAL-COMPLEXES; DENSITY-FUNCTIONAL THEORY; EFFICIENT ENERGY-TRANSFER; MIXED-VALENCE; EXCITED-STATE; CHARGE-TRANSFER; DELOCALIZED TRANSITION; MULLIKEN-HUSH; ACCEPTOR; RUTHENIUM(II);

D O I：

10.1002/chem.202402700

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Visible-light excitation of a family of bimetallic ruthenium polypyridines with the formula [RuII(tpy)(bpy)(-CN)RuII(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.

引用

页数：8

共 71 条

[1] A Hole Delocalization Strategy: Photoinduced Mixed-Valence MLCT States Featuring Extended Lifetimes [J].