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Distance Dependence of Bidirectional Concerted Proton–Electron Transfer in Phenol-Ru(2,2′-bipyridine)32+ Dyads

Chen, Jing and Kuss-Petermann, Martin and Wenger, Oliver S.. (2014) Distance Dependence of Bidirectional Concerted Proton–Electron Transfer in Phenol-Ru(2,2′-bipyridine)32+ Dyads. Chemistry - A European Journal, 20 (14). pp. 4098-4104.

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Official URL: http://edoc.unibas.ch/dok/A6254452

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Abstract

Proton-coupled electron transfer (PCET) was investigated in three covalent donor–bridge–acceptor molecules with different bridge lengths. Upon photoexcitation of their Ru(bpy)32+ (bpy=2,2′-bipyridine) photosensitizer in acetonitrile, intramolecular long-range electron transfer from a phenolic unit to Ru(bpy)32+ occurs in concert with release of the phenolic proton to pyrrolidine base. The kinetics of this bidirectional concerted proton–electron transfer (CPET) reaction were studied as a function of phenol–Ru(bpy)32+ distance by increasing the number of bridging p-xylene units. A distance decay constant (β) of 0.67±0.23 Å−1 was determined. The distance dependence of the rates for CPET is thus not significantly steeper than that for ordinary (i.e., not proton coupled) electron transfer across the same bridges, despite the concerted motion of oppositely charged particles into different directions. Long-range bidirectional CPET is an important reaction in many proteins and plays a key role in photosynthesis; our results are relevant in the context of photoinduced separation of protons and electrons as a means of light-to-chemical energy conversion. This is the first determination of β for a bidirectional CPET reaction.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Kuss-Petermann, Martin and Chen, Jing
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Wiley
ISSN:0947-6539
e-ISSN:1521-3765
Note:Publication type according to Uni Basel Research Database: Journal article -- The final publication is available at Wiley, see DOI link
Language:English
Identification Number:
Last Modified:11 Jun 2018 09:49
Deposited On:23 May 2014 08:34

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