Demonstration of Baird's rule complementarity in the singlet state with implications for excited-state intramolecular proton transfer

dc.contributor.author Lampkin, Bryan
dc.contributor.author VanVeller, Brett
dc.contributor.author Nguyen, Yen
dc.contributor.author Karadakov, Peter
dc.contributor.author VanVeller, Brett
dc.contributor.department Chemistry
dc.date 2020-12-04T03:15:06.000
dc.date.accessioned 2021-02-24T22:52:00Z
dc.date.available 2021-02-24T22:52:00Z
dc.date.copyright Tue Jan 01 00:00:00 UTC 2019
dc.date.issued 2019-01-01
dc.description.abstract <p>The aromatic character of an arene is proposed to switch from aromatic in the ground state (S0) to antiaromatic in the S1 and T1 excited states. This behavior is known as Baird's rule and has been invoked to explain excited-state properties, primarily in the triplet state, whereas rationalization of antiaromaticity in the singlet state is less developed. This work demonstrates the first application of Baird's rule to rationalize previously unexplained experimental behavior of the singlet state process known as excited-state intramolecular proton transfer (ESIPT). Further, by analyzing the variations in isotropic magnetic shielding around the base arenes (benzene and naphthalene) of ESIPT fluorophores in the S0 and S1 electronic states, different shielding distributions indicate a complementarity to Baird's rule: greater aromaticity in S0 leads to greater antiaromaticity in S1 and vice versa. These findings have immediate application in the design of functional ESIPT fluorophores and, more generally, for photochemical reactions that are driven by the relief of antiaromaticity in the excited state. Notably, a tenet of traditional chromophore design states that expansion of conjugation generally leads to a red-shift in absorbance and emission wavelengths. The results of this study show that ESIPT fluorophores run contrary to those conventional design principles and this behavior can only be rationalized by considering Baird's rule.</p>
dc.description.comments <p>This article is published as Lampkin, Bryan J., Yen H. Nguyen, Peter B. Karadakov, and Brett VanVeller. "Demonstration of Baird's rule complementarity in the singlet state with implications for excited-state intramolecular proton transfer." <em>Physical Chemistry Chemical Physics</em> 21, no. 22 (2019): 11608-11614. DOI: <a href="https://doi.org/10.1039/C9CP02050K" target="_blank">10.1039/C9CP02050K</a>. Posted with permission.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/chem_pubs/1274/
dc.identifier.articleid 2280
dc.identifier.contextkey 20396437
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath chem_pubs/1274
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/93651
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/1274/2019_VanVellerBrett_DemonstrationBairds.pdf|||Fri Jan 14 19:28:53 UTC 2022
dc.source.uri 10.1039/C9CP02050K
dc.subject.disciplines Physical Chemistry
dc.title Demonstration of Baird's rule complementarity in the singlet state with implications for excited-state intramolecular proton transfer
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication d1499866-e3f1-4b38-b90b-bcf0c52d8b79
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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