Tuning Electron-Transfer Driving Force in Photosynthetic Special Pair Models

Ramírez-Wierzbicki I, Sanchez Merlinsky L, Pieslinger GE, Domínguez S, Slep LD, Baraldo LM, Cadranel A (2024)

Publication Type: Journal article

Publication year: 2024

Journal

Chemistry - A European Journal Wiley

DOI: 10.1002/chem.202402700

Abstract

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.

Authors with CRIS profile

Alejandro Cadranel

Involved external institutions

Universidad de Buenos Aires (UBA) / University of Buenos Aires AR Argentina (AR)

How to cite

APA:

Ramírez-Wierzbicki, I., Sanchez Merlinsky, L., Pieslinger, G.E., Domínguez, S., Slep, L.D., Baraldo, L.M., & Cadranel, A. (2024). Tuning Electron-Transfer Driving Force in Photosynthetic Special Pair Models. Chemistry - A European Journal. https://doi.org/10.1002/chem.202402700

MLA:

Ramírez-Wierzbicki, Ivana, et al. "Tuning Electron-Transfer Driving Force in Photosynthetic Special Pair Models." Chemistry - A European Journal (2024).

BibTeX: Download