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Solvent-Mediated Activation/Deactivation of Photoinduced Electron-Transfer in a Molecular Dyad

Larsen, Christopher B. and Farrow, George A. and Smith, Lian D. and Appleby, Martin and Chekulaev, Dimitri and Weinstein, Julia and Wenger, Oliver S.. (2020) Solvent-Mediated Activation/Deactivation of Photoinduced Electron-Transfer in a Molecular Dyad. Inorganic Chemistry, 59 (15). pp. 10430-10438.

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Abstract

Herein is presented a molecular dyad comprised of a [Ru(bpy)3]2+ photosensitizer and an anthraquinone (AQ) acceptor coupled by an ethynyl linker ([Ru(bpy)2(bpy-cc-AQ)]2+) in which activation/deactivation of photoinduced electron-transfer from the [Ru(bpy)3]2+ photosensitizer to the AQ acceptor is achieved and characterized as a function of the dielectric constant and hydrogen-bond donating ability of the solvent used. It is demonstrated that the rate of photoinduced electron-transfer can be modulated over several orders of magnitude (105-1011 s-1) by choice of solvent. Nanosecond transient absorption spectra are dominated by MLCT signals and exhibit identical decay kinetics to the corresponding emission signals. Ultrafast transient absorption and time-resolved infrared spectroscopies provide direct evidence for the formation of the charge-separated (CS) state and rapid (on the order of a few picoseconds) establishment of an excited-state pseudoequilibrium.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Larsen, Christopher Bryan
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0020-1669
e-ISSN:1520-510X
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:12 Aug 2020 15:53
Deposited On:12 Aug 2020 15:53

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