Long-range proton-coupled electron transfer in phenol-[Ru(2,2'-bipyrazine)3]3+ dyads

Bronner, Catherine and Wenger, Oliver S.. (2014) Long-range proton-coupled electron transfer in phenol-[Ru(2,2'-bipyrazine)3]3+ dyads. Physical Chemistry Chemical Physics, 16 (8). pp. 3617-3622.

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Official URL: http://edoc.unibas.ch/dok/A6254451

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Two dyads in which either 4-cyanophenol or un-substituted phenol is connected via a p-xylene spacer to a Ru(bpz)32+ (bpz = 2,2′-bipyrazine) complex were synthesized and investigated. Selective photo-excitation of Ru(bpz)32+ at 532 nm in a CH3CN–H2O mixture leads to the formation of 4-cyanophenolate or phenolate along with Ru(bpz)32+ in its electronic ground state. This apparent photoacid behavior can be understood on the basis of a reaction sequence comprised of an initial photoinduced proton-coupled electron transfer (PCET) during which 4-cyanophenol or phenol is oxidized and deprotonated, followed by a thermal electron transfer event in the course of which 4-cyanophenoxyl or phenoxyl is reduced by Ru(bpz)3+ to 4-cyanophenolate or phenolate. Conceptually, this reaction sequence is identical to a sequence of photoinduced charge-separation and thermal charge-recombination events as observed previously for many electron transfer dyads, with the important difference that the initial photoinduced electron transfer process is proton-coupled. The dyad containing 4-cyanophenol reacts via concerted-proton electron transfer (CPET) whereas the dyad containing un-substituted phenol appears to react predominantly via a stepwise PCET mechanism. Long-range PCET is a key reaction in photosystem II. Understanding the factors that govern the kinetics of long-range PCET is desirable in the broader context of light-to-energy conversion by means of proton–electron separation across natural or artificial membranes.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Bronner, Catherine
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
Note:Publication type according to Uni Basel Research Database: Journal article
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edoc DOI:
Last Modified:03 May 2017 11:57
Deposited On:23 May 2014 08:34

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