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Journal ArticleDOI

Excited-state quenching by proton-coupled electron transfer

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TLDR
The protonated, reduced complex [Ru(bpy)2(bpzH•)]2+ functions as a H-atom reductant toward quinone or benzaldehyde with potential implications for net photochemistry and energy conversion.
Abstract
The emitting metal-to-ligand charge transfer (MLCT) excited state of [Ru(bpy)2(bpz)]2+ (bpy is 2,2‘-bipyridine; bpz is 2,2‘-bipyrazine) is reductively quenched by hydroquinone (H2Q) by proton-coupled electron transfer (PCET), most likely by concerted electron−proton transfer (EPT). The identity of the transient products ([Ru(bpy)2(bpzH•)]2+ and HQ•) and the kinetics of their formation and disappearance have been established by steady-state emission and time-resolved emission, absorption, and EPR measurements. The protonated, reduced complex [Ru(bpy)2(bpzH•)]2+ functions as a H-atom reductant toward quinone or benzaldehyde with potential implications for net photochemistry and energy conversion.

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Citations
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Journal ArticleDOI

Role of solvent dynamics in ultrafast photoinduced proton-coupled electron transfer reactions in solution.

TL;DR: These model studies illustrate how the coupling between the electron-proton transfer and the solvent dynamics can be tuned by altering the solute and solvent properties.
Journal ArticleDOI

Proton-coupled electron transfer originating from excited states of luminescent transition-metal complexes.

TL;DR: The present minireview differs from other reviews on the subject of PCET in that it focuses specifically on reactions occurring directly from electronically excited states.
Journal ArticleDOI

Proton-coupled electron transfer with photoexcited ruthenium(II), rhenium(I), and iridium(III) complexes

TL;DR: The field of excited-state proton-coupled electron transfer (PCET) with d6 metal complexes is reviewed in this paper, which aims to illustrate the usefulness of such complexes for mechanistic studies of excitedstate PCET.
Journal ArticleDOI

Photo-induced proton-coupled electron transfer reactions of acridine orange: comprehensive spectral and kinetics analysis.

TL;DR: Enhanced optical tracking, along with excited- state thermochemical analysis, facilitates assignment of the mechanism of excited-state PCET reactivity.
Journal ArticleDOI

Influence of Donor-Acceptor Distance Variation on Photoinduced Electron and Proton Transfer in Rhenium(I)-Phenol Dyads

TL;DR: It is demonstrated that electronically strongly coupled donor-acceptor systems may exhibit significantly different photoinduced PCET chemistry than electronically weakly coupling donor-bridge- acceptor molecules.
References
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Journal ArticleDOI

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Journal ArticleDOI

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TL;DR: Intrinsic barriers for PCET can be comparable to or larger than those for ET, and many PCET/HAT rate constants are predicted well by the Marcus cross relation.
Journal ArticleDOI

Theoretical Perspectives on Proton-Coupled Electron Transfer Reactions

TL;DR: This theoretical framework allows predictions of rates, mechanisms, and kinetic isotope effects for proton-coupled electron transfer reactions.
Journal ArticleDOI

Oxygen Production in Nature: A Light-Driven Metalloradical Enzyme Process

TL;DR: The physical structure and energetics of PSII are reviewed and a metalloradical enzyme mechanism for the water-oxidation process it catalyzes is discussed, which is based on the specifics of the chemistry in which O2 participates.
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