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Title: Proton-Coupled Electron Transfer in a Strongly Coupled Photosystem II-Inspired Chromophore–Imidazole–Phenol Complex: Stepwise Oxidation and Concerted Reduction

Abstract

Proton-coupled electron-transfer (PCET) reactions were studied in acetonitrile for a Photosystem II (PSII) inspired [Ru(bpy)2(phen-imidazole-Ph(OH)(tBu)2)]2+, in which Ru(III) generated by a flash-quench sequence oxidizes the appended phenol and the proton is transferred to the hydrogen bonded imidazole base. In contrast to related systems, the donor and acceptor are strongly coupled, as indicated by the shift in the RuIII/IIcouple upon phenol oxidation, and intramolecular oxidation of the phenol by Ru(III) is energetically favorable by both stepwise or concerted pathways. The phenol oxidation occurs via a stepwise ET-PT mechanism with kET = 2.7 × 107 s₋1 and a kinetic isotope effect (KIE) of 0.99 ± 0.03. The electron transfer reaction was characterized as adiabatic with λDA = 1.16 eV and 280 < HDA < 540 cm₋1 consistent with strong electronic coupling and slow solvent dynamics. Reduction of the phenoxyl radical by the quencher radical was examined as the analogue of the redox reaction between the PSII tyrosyl radical and the oxygen evolving complex (OEC). In our PSII-inspired complex, the recombination reaction activation energy is < 2 kcal mol₋1. In conclusion, the reaction is nonadiabatic (VPCET ~ 22 cm₋1 (H) and 49 cm₋1 (D)), concerted, and exhibits an unexpected inverse KIE of 0.55more » that is attributed to greater overlap of the reactant vibronic ground state with the OD vibronic states of the proton acceptor due to the smaller quantum spacing of the deuterium vibrational levels.« less

Authors:
 [1];  [1];  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1336211
Report Number(s):
BNL-113231-2016-JA
Journal ID: ISSN 0002-7863; R&D Project: CO026; KC0304030
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 36; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Manbeck, Gerald F., Fujita, Etsuko, and Concepcion, Javier J. Proton-Coupled Electron Transfer in a Strongly Coupled Photosystem II-Inspired Chromophore–Imidazole–Phenol Complex: Stepwise Oxidation and Concerted Reduction. United States: N. p., 2016. Web. doi:10.1021/jacs.6b03506.
Manbeck, Gerald F., Fujita, Etsuko, & Concepcion, Javier J. Proton-Coupled Electron Transfer in a Strongly Coupled Photosystem II-Inspired Chromophore–Imidazole–Phenol Complex: Stepwise Oxidation and Concerted Reduction. United States. https://doi.org/10.1021/jacs.6b03506
Manbeck, Gerald F., Fujita, Etsuko, and Concepcion, Javier J. Thu . "Proton-Coupled Electron Transfer in a Strongly Coupled Photosystem II-Inspired Chromophore–Imidazole–Phenol Complex: Stepwise Oxidation and Concerted Reduction". United States. https://doi.org/10.1021/jacs.6b03506. https://www.osti.gov/servlets/purl/1336211.
@article{osti_1336211,
title = {Proton-Coupled Electron Transfer in a Strongly Coupled Photosystem II-Inspired Chromophore–Imidazole–Phenol Complex: Stepwise Oxidation and Concerted Reduction},
author = {Manbeck, Gerald F. and Fujita, Etsuko and Concepcion, Javier J.},
abstractNote = {Proton-coupled electron-transfer (PCET) reactions were studied in acetonitrile for a Photosystem II (PSII) inspired [Ru(bpy)2(phen-imidazole-Ph(OH)(tBu)2)]2+, in which Ru(III) generated by a flash-quench sequence oxidizes the appended phenol and the proton is transferred to the hydrogen bonded imidazole base. In contrast to related systems, the donor and acceptor are strongly coupled, as indicated by the shift in the RuIII/IIcouple upon phenol oxidation, and intramolecular oxidation of the phenol by Ru(III) is energetically favorable by both stepwise or concerted pathways. The phenol oxidation occurs via a stepwise ET-PT mechanism with kET = 2.7 × 107 s₋1 and a kinetic isotope effect (KIE) of 0.99 ± 0.03. The electron transfer reaction was characterized as adiabatic with λDA = 1.16 eV and 280 < HDA < 540 cm₋1 consistent with strong electronic coupling and slow solvent dynamics. Reduction of the phenoxyl radical by the quencher radical was examined as the analogue of the redox reaction between the PSII tyrosyl radical and the oxygen evolving complex (OEC). In our PSII-inspired complex, the recombination reaction activation energy is < 2 kcal mol₋1. In conclusion, the reaction is nonadiabatic (VPCET ~ 22 cm₋1 (H) and 49 cm₋1 (D)), concerted, and exhibits an unexpected inverse KIE of 0.55 that is attributed to greater overlap of the reactant vibronic ground state with the OD vibronic states of the proton acceptor due to the smaller quantum spacing of the deuterium vibrational levels.},
doi = {10.1021/jacs.6b03506},
journal = {Journal of the American Chemical Society},
number = 36,
volume = 138,
place = {United States},
year = {2016},
month = {8}
}

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Chart 1 Chart 1: Examples of Photo-Oxidation of Tyrosine-Histidine Mimics

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