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Excited-state proton transfer relieves antiaromaticity in molecules
Univ Houston, Dept Chem, Univ Pk, Houston, TX 77004 USA.
Univ Houston, Dept Chem, Univ Pk, Houston, TX 77004 USA.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Synthetic Molecular Chemistry.ORCID iD: 0000-0001-8076-1165
Univ Houston, Dept Chem, Univ Pk, Houston, TX 77004 USA.
2019 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 116, no 41, p. 20303-20308Article in journal (Refereed) Published
Abstract [en]

Baird’s rule explains why and when excited-state proton transfer (ESPT) reactions happen in organic compounds. Bifunctional compounds that are [4n + 2] π-aromatic in the ground state, become [4n + 2] π-antiaromatic in the first 1ππ* states, and proton transfer (either inter- or intramolecularly) helps relieve excited-state antiaromaticity. Computed nucleus-independent chemical shifts (NICS) for several ESPT examples (including excited-state intramolecular proton transfers (ESIPT), biprotonic transfers, dynamic catalyzed transfers, and proton relay transfers) document the important role of excited-state antiaromaticity. o-Salicylic acid undergoes ESPT only in the “antiaromatic” S1 (1ππ*) state, but not in the “aromatic” S2 (1ππ*) state. Stokes’ shifts of structurally related compounds [e.g., derivatives of 2-(2-hydroxyphenyl)benzoxazole and hydrogen-bonded complexes of 2-aminopyridine with protic substrates] vary depending on the antiaromaticity of the photoinduced tautomers. Remarkably, Baird’s rule predicts the effect of light on hydrogen bond strengths; hydrogen bonds that enhance (and reduce) excited-state antiaromaticity in compounds become weakened (and strengthened) upon photoexcitation.

Place, publisher, year, edition, pages
National Academy of Sciences , 2019. Vol. 116, no 41, p. 20303-20308
Keywords [en]
excited-state proton transfer, Baird's rule, aromaticity, antiaromaticity, hydrogen bonding
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-396721DOI: 10.1073/pnas.1908516116ISI: 000489770700015PubMedID: 31554699OAI: oai:DiVA.org:uu-396721DiVA, id: diva2:1375956
Funder
Swedish Research Council, 2015-04538NIH (National Institute of Health), R35GM133548Available from: 2019-12-06 Created: 2019-12-06 Last updated: 2019-12-12Bibliographically approved

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