Light induced manganese oxidation and long-lived charge separation in a Mn2 II,II-RuII(bpy)3-acceptor triad

Magnus Borgström, Nizamuddin Shaikh, Olof Johansson, Magnus F. Anderlund, Stenbjörn Styring, Björn Åkermark, Ann Magnuson, Leif Hammarström

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Abstract

The photoinduced electron-transfer reactions in a Mn2 II,II-RuII-NDI triad (1) ([Mn2(bpmp)(OAc) 2]+, bpmp = 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4- methylphenolate and OAc = acetate, RuII = tris-bipyridine ruthenium(II), and NDI = naphthalenediimide) have been studied by time-resolved optical and EPR spectroscopy. Complex 1 is the first synthetically linked electron donor-sensitizer-acceptor triad in which a manganese complex plays the role of the donor. EPR spectroscopy was used to directly demonstrate the light induced formation of both products: the oxidized manganese dimer complex (Mn2 II,III) and the reduced naphthalenediimide (NDI .-) acceptor moieties, while optical spectroscopy was used to follow the kinetic evolution of the [Ru(bpy)3]2+ intermediate states and the NDI.- radical in a wide temperature range. The average lifetime of the NDI.- radical is ca. 600 μs at room temperature, which is at least 2 orders of magnitude longer than that for previously reported triads based on a [Ru(bpy)3]2+ photosensitizer. At 140 K, this intramolecular recombination was dramatically slowed, displaying a lifetime of 0.1-1 s, which is comparable to many of the naturally occurring charge-separated states in photosynthetic reaction centra. It was found that the long recombination lifetime could be explained by an unusually large reorganization energy (λ ≈ 2.0 eV), due to a large inner reorganization of the manganese complex. This makes the recombination reaction strongly activated despite the large driving force (-ΔG° = 1.07 eV). Thus, the intrinsic properties of the manganese complex are favorable for creating a long-lived charge separation in the "Marcus normal region" also when the charge separated state energy is high.

Original languageEnglish
Pages (from-to)17504-17515
Number of pages12
JournalJournal of the American Chemical Society
Volume127
Issue number49
DOIs
Publication statusPublished - Dec 14 2005

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Manganese
Genetic Recombination
Light
Spectrum Analysis
Oxidation
Paramagnetic resonance
Spectroscopy
Electrons
Temperature
Photosensitizing Agents
Photosensitizers
Ruthenium
Gravitation
Dimers
Electron energy levels
Acetates
Kinetics
bis(bipyridyl)ruthenium(II)
naphthalenediimide
tris(2,2'-bipyridine)ruthenium II

ASJC Scopus subject areas

  • Chemistry(all)

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Light induced manganese oxidation and long-lived charge separation in a Mn2 II,II-RuII(bpy)3-acceptor triad. / Borgström, Magnus; Shaikh, Nizamuddin; Johansson, Olof; Anderlund, Magnus F.; Styring, Stenbjörn; Åkermark, Björn; Magnuson, Ann; Hammarström, Leif.

In: Journal of the American Chemical Society, Vol. 127, No. 49, 14.12.2005, p. 17504-17515.

Research output: Contribution to journalArticle

Borgström, M, Shaikh, N, Johansson, O, Anderlund, MF, Styring, S, Åkermark, B, Magnuson, A & Hammarström, L 2005, 'Light induced manganese oxidation and long-lived charge separation in a Mn2 II,II-RuII(bpy)3-acceptor triad', Journal of the American Chemical Society, vol. 127, no. 49, pp. 17504-17515. https://doi.org/10.1021/ja055243b
Borgström, Magnus ; Shaikh, Nizamuddin ; Johansson, Olof ; Anderlund, Magnus F. ; Styring, Stenbjörn ; Åkermark, Björn ; Magnuson, Ann ; Hammarström, Leif. / Light induced manganese oxidation and long-lived charge separation in a Mn2 II,II-RuII(bpy)3-acceptor triad. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 49. pp. 17504-17515.
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abstract = "The photoinduced electron-transfer reactions in a Mn2 II,II-RuII-NDI triad (1) ([Mn2(bpmp)(OAc) 2]+, bpmp = 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4- methylphenolate and OAc = acetate, RuII = tris-bipyridine ruthenium(II), and NDI = naphthalenediimide) have been studied by time-resolved optical and EPR spectroscopy. Complex 1 is the first synthetically linked electron donor-sensitizer-acceptor triad in which a manganese complex plays the role of the donor. EPR spectroscopy was used to directly demonstrate the light induced formation of both products: the oxidized manganese dimer complex (Mn2 II,III) and the reduced naphthalenediimide (NDI .-) acceptor moieties, while optical spectroscopy was used to follow the kinetic evolution of the [Ru(bpy)3]2+ intermediate states and the NDI.- radical in a wide temperature range. The average lifetime of the NDI.- radical is ca. 600 μs at room temperature, which is at least 2 orders of magnitude longer than that for previously reported triads based on a [Ru(bpy)3]2+ photosensitizer. At 140 K, this intramolecular recombination was dramatically slowed, displaying a lifetime of 0.1-1 s, which is comparable to many of the naturally occurring charge-separated states in photosynthetic reaction centra. It was found that the long recombination lifetime could be explained by an unusually large reorganization energy (λ ≈ 2.0 eV), due to a large inner reorganization of the manganese complex. This makes the recombination reaction strongly activated despite the large driving force (-ΔG° = 1.07 eV). Thus, the intrinsic properties of the manganese complex are favorable for creating a long-lived charge separation in the {"}Marcus normal region{"} also when the charge separated state energy is high.",
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AU - Shaikh, Nizamuddin

AU - Johansson, Olof

AU - Anderlund, Magnus F.

AU - Styring, Stenbjörn

AU - Åkermark, Björn

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