Discovery and characterization of an acridine radical photoreductant

MacKenzie, Ian A.; Wang, Leifeng; Onuska, Nicholas R.; Williams, Olivia F.; Begam, Khadiza; Moran, Andrew M.; Dunietz, Barry D.; Nicewicz, David A.

doi:10.1038/s41586-020-2131-1

Discovery and characterization of an acridine radical photoreductant

Journal Article · Wed Apr 01 00:00:00 EDT 2020 · Nature (London)

DOI:https://doi.org/10.1038/s41586-020-2131-1· OSTI ID:1801398

MacKenzie, Ian A. ^[1]; Wang, Leifeng ^[2]; Onuska, Nicholas R. ^[2]; Williams, Olivia F. ^[2]; Begam, Khadiza ^[3]; Moran, Andrew M. ^[2]; Dunietz, Barry D. ^[3]; ^[2]

Univ. of North Carolina, Chapel Hill, NC (United States); Kent State University
Univ. of North Carolina, Chapel Hill, NC (United States)
Kent State Univ., Kent, OH (United States)

Not provided.Photoinduced electron transfer (PET) is a phenomenon whereby the absorption of light by a chemical species provides an energetic driving force for an electron-transfer reaction. This mechanism is relevant in many areas of chemistry, including the study of natural and artificial photosynthesis, photovoltaics and photosensitive materials. In recent years, research in the area of photoredox catalysis has enabled the use of PET for the catalytic generation of both neutral and charged organic free-radical species. These technologies have enabled previously inaccessible chemical transformations and have been widely used in both academic and industrial settings. Such reactions are often catalysed by visible-light-absorbing organic molecules or transition-metal complexes of ruthenium, iridium, chromium or copper. Although various closed-shell organic molecules have been shown to behave as competent electron-transfer catalysts in photoredox reactions, there are only limited reports of PET reactions involving neutral organic radicals as excited-state donors or acceptors. This is unsurprising because the lifetimes of doublet excited states of neutral organic radicals are typically several orders of magnitude shorter than the singlet lifetimes of known transition-metal photoredox catalysts. Here we document the discovery, characterization and reactivity of a neutral acridine radical with a maximum excited-state oxidation potential of -3.36 volts versus a saturated calomel electrode, which is similarly reducing to elemental lithium, making this radical one of the most potent chemical reductants reported. Spectroscopic, computational and chemical studies indicate that the formation of a twisted intramolecular charge-transfer species enables the population of higher-energy doublet excited states, leading to the observed potent photoreducing behaviour. Finally, we demonstrate that this catalytically generated PET catalyst facilitates several chemical reactions that typically require alkali metal reductants and can be used in other organic transformations that require dissolving metal reductants.

View Accepted Manuscript (DOE)

Research Organization:: Kent State Univ., Kent, OH (United States); Univ. of North Carolina, Chapel Hill, NC (United States)

Sponsoring Organization:: National Institutes of Health (NIH); National Natural Science Foundation of China (NSFC); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0001011; SC0016501

OSTI ID:: 1801398

Journal Information:: Nature (London), Journal Name: Nature (London) Journal Issue: 7801 Vol. 580; ISSN 0028-0836

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Discovery and characterization of an acridine radical photoreductant

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