Photoinduced
Electron Transfer Coupled to Donor Deprotonation
and Acceptor Protonation in a Molecular Triad Mimicking Photosystem
II
Posted on 2017-09-14 - 15:20
The
first artificial donor–sensitizer–acceptor compound
in which photoinduced long-range electron transfer is coupled to donor
deprotonation and acceptor protonation is reported. The long-lived
photoproduct stores energy in the form of a radical pair state in
which the charges of the donor and the acceptor remain unchanged,
much in contrast to previously investigated systems that exhibit charge-separated
states comprised of electron–hole pairs. This finding is relevant
for light-driven accumulation of redox equivalents, because it exemplifies
how the buildup of charge can be avoided yet light energy can be stored.
Proton-coupled electron transfer (PCET) reactions at a phenol donor
and a monoquat acceptor triggered by excitation of a Ru(II) sensitizer
enable this form of photochemical energy storage. Our triad emulates
photosystem II more closely than previously investigated systems,
because tyrosine Z is oxidized and deprotonated, whereas plastoquinone
B is reduced and protonated.
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Pannwitz, Andrea; Wenger, Oliver S. (2017). Photoinduced
Electron Transfer Coupled to Donor Deprotonation
and Acceptor Protonation in a Molecular Triad Mimicking Photosystem
II. ACS Publications. Collection. https://doi.org/10.1021/jacs.7b08761
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AUTHORS (2)
AP
Andrea Pannwitz
OW
Oliver S. Wenger
KEYWORDS
PCETdonor deprotonationenergy storageDonor Deprotonationacceptor protonationexhibit charge-separated statesProton-coupled electron transferlight-driven accumulationlight energytyrosine Zpair statephenol donorplastoquinone Btriad emulates photosystem IIredox equivalentsAcceptor Protonationelectron transferPhotoinduced Electron Transfermonoquat acceptorphotoproduct stores energyMolecular Triad Mimicking Photosystem II