TY - JOUR
T1 - Completing a Charge Transport Chain for Artificial Photosynthesis
AU - Eberhart, Michael S.
AU - Bowers, Leah M.Rader
AU - Shan, Bing
AU - Troian-Gautier, Ludovic
AU - Kyle Brennaman, M.
AU - Papanikolas, John M.
AU - Meyer, Thomas J.
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/8/8
Y1 - 2018/8/8
N2 - A ruthenium polypyridyl chromophore with electronically isolated triarylamine substituents has been synthesized that models the role of tyrosine in the electron transport chain in photosystem II. When bound to the surface of a TiO2 electrode, electron injection from a Ru(II) Metal-to-Ligand Charge Transfer (MLCT) excited state occurs from the complex to the electrode to give Ru(III). Subsequent rapid electron transfer from the pendant triarylamine to Ru(III) occurs with an observed rate constant of 1010 s-1, which is limited by the rate of electron injection into the semiconductor. Transfer of the oxidative equivalent away from the semiconductor surface results in dramatically reduced rates of back electron transfer, and a long-lived (= 165 μs) triarylamine radical cation that has been used to oxidize hydroquinone to quinone in solution.
AB - A ruthenium polypyridyl chromophore with electronically isolated triarylamine substituents has been synthesized that models the role of tyrosine in the electron transport chain in photosystem II. When bound to the surface of a TiO2 electrode, electron injection from a Ru(II) Metal-to-Ligand Charge Transfer (MLCT) excited state occurs from the complex to the electrode to give Ru(III). Subsequent rapid electron transfer from the pendant triarylamine to Ru(III) occurs with an observed rate constant of 1010 s-1, which is limited by the rate of electron injection into the semiconductor. Transfer of the oxidative equivalent away from the semiconductor surface results in dramatically reduced rates of back electron transfer, and a long-lived (= 165 μs) triarylamine radical cation that has been used to oxidize hydroquinone to quinone in solution.
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U2 - 10.1021/jacs.8b06740
DO - 10.1021/jacs.8b06740
M3 - Article
C2 - 30036057
AN - SCOPUS:85050814905
SN - 0002-7863
VL - 140
SP - 9823
EP - 9826
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 31
ER -