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.
UR - http://www.scopus.com/inward/record.url?scp=85064980973&partnerID=8YFLogxK
U2 - 10.1021/jacs.9b02517
DO - 10.1021/jacs.9b02517
M3 - Article
C2 - 30943724
AN - SCOPUS:85064980973
SN - 0002-7863
VL - 141
SP - 6748
EP - 6754
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 16
ER -