Modulation of intramolecular Fe oxidation with distance and driving force in Ru-Fe photocatalysts

In this paper we have investigated the efficiency of the intramolecular electron transfer process in a family of Ru II -Fe II dyads, previously shown to perform the light-driven activation of an iron-bound water molecule. The Ru chromophore and Fe catalytic units are connected at different lengths t...

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Bibliographic Details
Published in:New journal of chemistry 2024-10, Vol.48 (39), p.1727-1737
Main Authors: Herrero, Christian, Banse, Frédéric, Leibl, Winfried, Quaranta, Annamaria
Format: Article
Language:English
Subjects:
Charge transfer
Chromophores
Coupling (molecular)
Design optimization
Electron transfer
Ethyl esters
Iron
Oxidation
Parameter modification
Photocatalysts
Rate constants
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Summary:In this paper we have investigated the efficiency of the intramolecular electron transfer process in a family of Ru II -Fe II dyads, previously shown to perform the light-driven activation of an iron-bound water molecule. The Ru chromophore and Fe catalytic units are connected at different lengths through a triazole group attached to an alkyl chain containing either three or five carbon atoms. The driving force for Fe oxidation is modified by adding ethyl ester substituents on the bipyridines completing the coordination sphere of a [Ru(bpy) 3 ] 2+ -like chromophore. Transient absorption measurements and simulations were used to obtain the rate constants of internal charge transfer for the different complexes. The parameters governing the electron transfer process, reorganisation energy λ and electronic coupling H AB were obtained, and the observed variations are discussed within the framework of Marcus theory, which can help in understanding how to optimize the design of molecular photocatalysts. The intramolecular electron transfer process in four Ru-Fe dyads was investigated. Rates, electronic coupling and reorganisation energy are discussed in the frame of Marcus theory.
ISSN:1144-0546
1369-9261
DOI:10.1039/d4nj02755h