A Fine Line Separates Carbocations from Diradical Ions in Donor-Unconjugated Cations

dc.contributor.author Albright, Toshia
dc.contributor.author Winter, Arthur
dc.contributor.author Winter, Arthur
dc.contributor.department Chemistry
dc.date 2018-02-17T06:46:43.000
dc.date.accessioned 2020-06-30T01:17:55Z
dc.date.available 2020-06-30T01:17:55Z
dc.date.copyright Thu Jan 01 00:00:00 UTC 2015
dc.date.issued 2015-01-01
dc.description.abstract <p>Carbocations are traditionally thought to be closed-shell electrophiles featuring an empty orbital rich in p character. Here, density functional theory computations indicate that when strong π donors are not placed in direct conjugation with benzylic-type cations, alternative diradical configurations that resemble non-Kekulé diradicals are possible. For certain donor–acceptor frameworks, an open-shell singlet configuration is the computed ground state for the cation, whereas for coumarin and xanthenyl cations substituted with strong donors, a triplet diradical configuration is the computed ground state. Changing the substituent nature and attachment location substantially alters the energy gaps between the different electronic configurations and can manipulate the computed ground-state electronic configuration. There are few known examples of ground-state triplet carbocations, and, to our knowledge, no other examples of open-shell singlet carbocations. The open-shell singlet and triplet “carbocations” described here may have reactivity distinct from that of typical closed-shell singlet carbocations and, if appropriately stabilized, lead to organic materials with interesting electronic and magnetic properties.</p>
dc.description.comments <p>Reprinted (adapted) with permission from J. Am. Chem. Soc., 2015, 137 (9), pp 3402–3410. Copyright (YEAR) American Chemical Society.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/chem_pubs/144/
dc.identifier.articleid 1155
dc.identifier.contextkey 7886601
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath chem_pubs/144
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/14578
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/144/0-2015_Winter_FreeLine_License.pdf|||Fri Jan 14 20:19:33 UTC 2022
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/144/2015_Winter_FineLine.pdf|||Fri Jan 14 20:19:34 UTC 2022
dc.source.uri 10.1021/jacs.5b00707
dc.subject.disciplines Materials Chemistry
dc.subject.disciplines Other Chemistry
dc.subject.disciplines Physical Chemistry
dc.title A Fine Line Separates Carbocations from Diradical Ions in Donor-Unconjugated Cations
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication a2121da6-c591-494f-b9a9-595265e46ff9
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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