Photodriven Oxidation of Water by Plastoquinone Analogs with a Nonheme Iron Catalyst

Young Hyun Hong; Jieun Jung; Tatsuo Nakagawa; Namita Sharma; Yong Min Lee; Wonwoo Nam; Shunichi Fukuzumi

doi:10.1021/jacs.9b02517

Photodriven Oxidation of Water by Plastoquinone Analogs with a Nonheme Iron Catalyst

Young Hyun Hong, Jieun Jung, Tatsuo Nakagawa, Namita Sharma, Yong Min Lee, Wonwoo Nam, Shunichi Fukuzumi

Chemistry & Nanoscience

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

20 Scopus citations

Abstract

Photoirradiation of an acetonitrile solution containing p-benzoquinone derivatives (X-Q) as plastoquinone analogs, a nonheme iron(II) complex, [(N4Py)Fe^II]²⁺ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), and H₂O afforded the evolution of O₂ and the formation of the corresponding hydroquinone derivatives (X-QH₂) quantitatively. During the photodriven oxidation of water by X-Q, [(N4Py)Fe^II]²⁺ was oxidized by the excited state of X-Q to produce the iron(IV)-oxo complex ([(N4Py)Fe^IV(O)]²⁺) quantitatively. The concentration of [(N4Py)Fe^IV(O)]²⁺ remained virtually the same during the repeated cycles of photodriven oxidation of water by X-Q. [(N4Py)Fe^IV(O)]²⁺ was further oxidized by the excited state of X-Q to [(N4Py)Fe^V(O)]³⁺ this Fe^V-oxo species is proposed as an active oxidant that affects the water oxidation. The photocatalytic mechanism of the water oxidation by X-Q with [(N4Py)Fe^II]²⁺ was clarified by detecting intermediates using various spectroscopic techniques, such as transient absorption and electron paramagnetic resonance measurements. To the best of our knowledge, the present study reports the first example of a functional model of Photosystem II (PSII) using X-Q as plastoquinone analogs in the photocatalytic oxidation of water.

Original language	English
Pages (from-to)	6748-6754
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	141
Issue number	16
DOIs	https://doi.org/10.1021/jacs.9b02517
State	Published - 24 Apr 2019

Bibliographical note

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (no. 16H02268 to S.F.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to T.N. and S.F.) from Japan Science and Technology Agency (JST).

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program 2017R1D1A1B03029982 to Y.-M.L. and (2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (no. 16H02268 to S.F.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to T.N. and S.F.) from Japan Science and Technology Agency (JST).

Publisher Copyright:
© 2019 American Chemical Society.

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10.1021/jacs.9b02517

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@article{0ecc42b1d0594363a88b277644ebc7dc,

title = "Photodriven Oxidation of Water by Plastoquinone Analogs with a Nonheme Iron Catalyst",

abstract = "Photoirradiation of an acetonitrile solution containing p-benzoquinone derivatives (X-Q) as plastoquinone analogs, a nonheme iron(II) complex, [(N4Py)FeII]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), and H2O afforded the evolution of O2 and the formation of the corresponding hydroquinone derivatives (X-QH2) quantitatively. During the photodriven oxidation of water by X-Q, [(N4Py)FeII]2+ was oxidized by the excited state of X-Q to produce the iron(IV)-oxo complex ([(N4Py)FeIV(O)]2+) quantitatively. The concentration of [(N4Py)FeIV(O)]2+ remained virtually the same during the repeated cycles of photodriven oxidation of water by X-Q. [(N4Py)FeIV(O)]2+ was further oxidized by the excited state of X-Q to [(N4Py)FeV(O)]3+ this FeV-oxo species is proposed as an active oxidant that affects the water oxidation. The photocatalytic mechanism of the water oxidation by X-Q with [(N4Py)FeII]2+ was clarified by detecting intermediates using various spectroscopic techniques, such as transient absorption and electron paramagnetic resonance measurements. To the best of our knowledge, the present study reports the first example of a functional model of Photosystem II (PSII) using X-Q as plastoquinone analogs in the photocatalytic oxidation of water.",

author = "Hong, {Young Hyun} and Jieun Jung and Tatsuo Nakagawa and Namita Sharma and Lee, {Yong Min} and Wonwoo Nam and Shunichi Fukuzumi",

note = "Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (no. 16H02268 to S.F.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to T.N. and S.F.) from Japan Science and Technology Agency (JST). Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program 2017R1D1A1B03029982 to Y.-M.L. and (2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (no. 16H02268 to S.F.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to T.N. and S.F.) from Japan Science and Technology Agency (JST). Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = apr,

day = "24",

doi = "10.1021/jacs.9b02517",

language = "English",

volume = "141",

pages = "6748--6754",

journal = "Journal of the American Chemical Society",

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TY - JOUR

T1 - Photodriven Oxidation of Water by Plastoquinone Analogs with a Nonheme Iron Catalyst

AU - Hong, Young Hyun

AU - Jung, Jieun

AU - Nakagawa, Tatsuo

AU - Sharma, Namita

AU - Lee, Yong Min

AU - Nam, Wonwoo

AU - Fukuzumi, Shunichi

N1 - Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (no. 16H02268 to S.F.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to T.N. and S.F.) from Japan Science and Technology Agency (JST). Funding Information: This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program 2017R1D1A1B03029982 to Y.-M.L. and (2017R1D1A1B03032615 to S.F.). This work was also supported by Grants-in-Aid (no. 16H02268 to S.F.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), SENTAN project (to T.N. and S.F.) from Japan Science and Technology Agency (JST). Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/4/24

Y1 - 2019/4/24

N2 - Photoirradiation of an acetonitrile solution containing p-benzoquinone derivatives (X-Q) as plastoquinone analogs, a nonheme iron(II) complex, [(N4Py)FeII]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), and H2O afforded the evolution of O2 and the formation of the corresponding hydroquinone derivatives (X-QH2) quantitatively. During the photodriven oxidation of water by X-Q, [(N4Py)FeII]2+ was oxidized by the excited state of X-Q to produce the iron(IV)-oxo complex ([(N4Py)FeIV(O)]2+) quantitatively. The concentration of [(N4Py)FeIV(O)]2+ remained virtually the same during the repeated cycles of photodriven oxidation of water by X-Q. [(N4Py)FeIV(O)]2+ was further oxidized by the excited state of X-Q to [(N4Py)FeV(O)]3+ this FeV-oxo species is proposed as an active oxidant that affects the water oxidation. The photocatalytic mechanism of the water oxidation by X-Q with [(N4Py)FeII]2+ was clarified by detecting intermediates using various spectroscopic techniques, such as transient absorption and electron paramagnetic resonance measurements. To the best of our knowledge, the present study reports the first example of a functional model of Photosystem II (PSII) using X-Q as plastoquinone analogs in the photocatalytic oxidation of water.

AB - Photoirradiation of an acetonitrile solution containing p-benzoquinone derivatives (X-Q) as plastoquinone analogs, a nonheme iron(II) complex, [(N4Py)FeII]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), and H2O afforded the evolution of O2 and the formation of the corresponding hydroquinone derivatives (X-QH2) quantitatively. During the photodriven oxidation of water by X-Q, [(N4Py)FeII]2+ was oxidized by the excited state of X-Q to produce the iron(IV)-oxo complex ([(N4Py)FeIV(O)]2+) quantitatively. The concentration of [(N4Py)FeIV(O)]2+ remained virtually the same during the repeated cycles of photodriven oxidation of water by X-Q. [(N4Py)FeIV(O)]2+ was further oxidized by the excited state of X-Q to [(N4Py)FeV(O)]3+ this FeV-oxo species is proposed as an active oxidant that affects the water oxidation. The photocatalytic mechanism of the water oxidation by X-Q with [(N4Py)FeII]2+ was clarified by detecting intermediates using various spectroscopic techniques, such as transient absorption and electron paramagnetic resonance measurements. To the best of our knowledge, the present study reports the first example of a functional model of Photosystem II (PSII) using X-Q as plastoquinone analogs in the photocatalytic oxidation of water.

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DO - 10.1021/jacs.9b02517

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SN - 0002-7863

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EP - 6754

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 16

ER -

Photodriven Oxidation of Water by Plastoquinone Analogs with a Nonheme Iron Catalyst

Abstract

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