Electrode-Mediated Photochemical Disproportionation of a Polypyridylruthenium(II) Chromophore

Nicholas A. Zosel; Matthew T. Baldwin; Kai Uyeda; Clare G. Madden; Aaron H. Shoemaker; Michael G. Hill; Bryan M. Hunter

doi:10.1021/acs.inorgchem.5c00113

Electrode-Mediated Photochemical Disproportionation of a Polypyridylruthenium(II) Chromophore

Nicholas A. Zosel, Matthew T. Baldwin, Kai Uyeda, Clare G. Madden, Aaron H. Shoemaker, Michael G. Hill^*, Bryan M. Hunter^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

On a metallic electrode embedded within a Nafion film, excitation at 470 nm of Ru(bpy)₂(dppn)²⁺ (bpy = 2,2′-bipyridine; dppn = benzo[i]dipyrido[3,2-a:2′,3′-c]phenazine) produced photocurrents indicative of tunable charge transfer between the electrode and photosensitizer, with the direction and magnitude of current dependent on the applied bias potential. At a bias potential of 0.85 V vs dppn/dppn^•-, the oxidative and reductive photocurrents cancel, yielding no net current; transient spectroscopy under these conditions reveals the photoelectrochemical disproportionation of the sensitizer to Ru³⁺ and Ru⁺. The ∼2.8 eV photon energy could thus be coupled to the ground-state reduction potentials of the photosensitizer, simultaneously generating electrons and holes on a monolithic electrode at potentials milder than the formal potentials.

Original language	English (US)
Pages (from-to)	5811-5815
Number of pages	5
Journal	Inorganic chemistry
Volume	64
Issue number	12
DOIs	https://doi.org/10.1021/acs.inorgchem.5c00113
State	Published - Mar 31 2025

Funding

M.G.H. acknowledges support from the John Stauffer Charitable Trust. Elemental analysis was performed at the Northwestern University Quantitative Bio-element Imaging Center generously supported by the NIH under Grant S10OD020118.

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Electrode-Mediated Photochemical Disproportionation of a Polypyridylruthenium(II) Chromophore",

abstract = "On a metallic electrode embedded within a Nafion film, excitation at 470 nm of Ru(bpy)2(dppn)2+ (bpy = 2,2′-bipyridine; dppn = benzo[i]dipyrido[3,2-a:2′,3′-c]phenazine) produced photocurrents indicative of tunable charge transfer between the electrode and photosensitizer, with the direction and magnitude of current dependent on the applied bias potential. At a bias potential of 0.85 V vs dppn/dppn•-, the oxidative and reductive photocurrents cancel, yielding no net current; transient spectroscopy under these conditions reveals the photoelectrochemical disproportionation of the sensitizer to Ru3+ and Ru+. The ∼2.8 eV photon energy could thus be coupled to the ground-state reduction potentials of the photosensitizer, simultaneously generating electrons and holes on a monolithic electrode at potentials milder than the formal potentials.",

author = "Zosel, {Nicholas A.} and Baldwin, {Matthew T.} and Kai Uyeda and Madden, {Clare G.} and Shoemaker, {Aaron H.} and Hill, {Michael G.} and Hunter, {Bryan M.}",

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doi = "10.1021/acs.inorgchem.5c00113",

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T1 - Electrode-Mediated Photochemical Disproportionation of a Polypyridylruthenium(II) Chromophore

AU - Zosel, Nicholas A.

AU - Baldwin, Matthew T.

AU - Uyeda, Kai

AU - Madden, Clare G.

AU - Shoemaker, Aaron H.

AU - Hill, Michael G.

AU - Hunter, Bryan M.

PY - 2025/3/31

Y1 - 2025/3/31

N2 - On a metallic electrode embedded within a Nafion film, excitation at 470 nm of Ru(bpy)2(dppn)2+ (bpy = 2,2′-bipyridine; dppn = benzo[i]dipyrido[3,2-a:2′,3′-c]phenazine) produced photocurrents indicative of tunable charge transfer between the electrode and photosensitizer, with the direction and magnitude of current dependent on the applied bias potential. At a bias potential of 0.85 V vs dppn/dppn•-, the oxidative and reductive photocurrents cancel, yielding no net current; transient spectroscopy under these conditions reveals the photoelectrochemical disproportionation of the sensitizer to Ru3+ and Ru+. The ∼2.8 eV photon energy could thus be coupled to the ground-state reduction potentials of the photosensitizer, simultaneously generating electrons and holes on a monolithic electrode at potentials milder than the formal potentials.

AB - On a metallic electrode embedded within a Nafion film, excitation at 470 nm of Ru(bpy)2(dppn)2+ (bpy = 2,2′-bipyridine; dppn = benzo[i]dipyrido[3,2-a:2′,3′-c]phenazine) produced photocurrents indicative of tunable charge transfer between the electrode and photosensitizer, with the direction and magnitude of current dependent on the applied bias potential. At a bias potential of 0.85 V vs dppn/dppn•-, the oxidative and reductive photocurrents cancel, yielding no net current; transient spectroscopy under these conditions reveals the photoelectrochemical disproportionation of the sensitizer to Ru3+ and Ru+. The ∼2.8 eV photon energy could thus be coupled to the ground-state reduction potentials of the photosensitizer, simultaneously generating electrons and holes on a monolithic electrode at potentials milder than the formal potentials.

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Electrode-Mediated Photochemical Disproportionation of a Polypyridylruthenium(II) Chromophore

Abstract

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