Anti-Aromaticity Relief as an Approach to Stabilize Free Radicals

dc.contributor.author Zhang, Rui
dc.contributor.author Ellern, Arkady
dc.contributor.department Chemistry
dc.date.accessioned 2021-12-22T18:30:19Z
dc.date.available 2021-12-22T18:30:19Z
dc.date.issued 2021-11-15
dc.description.abstract A new strategy to stabilize free radicals electronically is described by conjugating formally antiaromatic substituents to the free radical. With an antiaromatic substituent, the radical acts as an electron sink to allow configuration mixing of a low-energy zwitterionic state that provides antiaromaticity relief to the substituent. A combination of X-ray crystallography, VT-EPR and VT-UV/Vis spectroscopy, as well as computational analysis, was used to investigate this phenomenon. We find that this strategy of antiaromaticity relief is successful at stabilizing radicals, but only if the antiaromatic substituent is constrained to be planar by synthetically imposed conformational restraints that enable state mixing. This work leads to the counterintuitive finding that increasing the antiaromaticity of the radical substituent leads to greater radical stability, providing proof of concept for a new stereoelectronic approach for stabilizing free radicals.
dc.description.comments This is the peer-reviewed version of the following article: Zhang, Rui, Arkady Ellern, and Arthur H. Winter. "Anti‐Aromaticity Relief as an Approach to Stabilize Free Radicals." Angewandte Chemie International Edition (2021)., which has been published in final form at DOI: 10.1002/anie.202110870. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. Copyright 2021 Wiley-VCHGmbH. Posted with permission.
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/JwjboZNw
dc.language.iso en_US
dc.publisher Wiley
dc.source.uri https://doi.org/10.1002/anie.202110870 *
dc.subject.disciplines DegreeDisciplines::Physical Sciences and Mathematics::Chemistry::Organic Chemistry
dc.title Anti-Aromaticity Relief as an Approach to Stabilize Free Radicals
dc.type Article
dspace.entity.type Publication
relation.isAuthorOfPublication a2121da6-c591-494f-b9a9-595265e46ff9
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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