NDLI: Combining energy and electron transfer in a supramolecular environment for the “green” generation and utilization of hydrated electrons through photoredox catalysis

Content Provider	Royal Society of Chemistry (RSC)
Author	Kerzig, Christoph Goez, Martin
Copyright Year	2016
Abstract	We present a new mechanism that sustainably produces hydrated electrons, i.e., extremely strong reductants, yet consumes only green photons (532 nm) and the bioavailable ascorbate as sacrificial donor. The mechanism couples an energy-transfer cycle, in which a light-harvesting ruthenium polypyridine complex absorbs a first photon and passes the excitation energy on to a pyrene-based redox catalyst, with an electron-transfer cycle, in which the resulting triplet is reductively quenched and the energy-rich aryl radical anion is finally ionized by a second photon. Thus separating the roles of primary and secondary absorber permitted choosing a redox catalyst with a nonabsorbing ground state but efficiently ionizable radical anion; the quantum yield of the ionization step in our complex mechanism surpasses that in a simple photoredox cycle featuring only the metal complex by a factor of four. We suppressed undesired cross reactions through the noncovalent interactions of an anionic micelle with the charges of the reactants, intermediates, and products: the cationic light-harvesting complex remains affixed to the micelle surface, which blocks the access of the negatively charged sacrificial donor, aryl radical anion and hydrated electron, but allows the pyrene ground-state almost unhindered entry into the Stern layer despite a carboxylate substituent by virtue of its large dipole moment. We demonstrate the applicability of the mechanism to the reductive detoxification of halogenated organic waste, which hitherto required UV-C for electron generation, by decomposing the typical model compound chloroacetate.
Starting Page	3862
Ending Page	3868
Page Count	7
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	7
Issue Number	6
Journal	Chemical Science
DOI	10.1039/c5sc04800a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Pyrene Ruthenium Electric dipole moment Ionization Double layer (surface science) Redox Micelle Substituent Photon Radical ion Quantum tunnelling Light-harvesting complex
Content Type	Text
Resource Type	Article
Subject	Chemistry

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