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Energetics of Baird aromaticity supported by inversion of photoexcited chiral [4n]annulene derivatives
Univ Tokyo, Dept Chem & Biotechnol, Sch Engn, Bunkyo Ku, 7-3-1 Hongo, Tokyo 1138656, Japan..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Yonsei Univ, Spect Lab Funct Elect Syst, Seoul 120749, South Korea.;Yonsei Univ, Dept Chem, Seoul 120749, South Korea..
Osaka Univ, Dept Appl Chem, Grad Sch Engn, 2-1 Yamada Oka, Suita, Osaka 5650871, Japan..
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2017 (English)In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723, Vol. 8, 346Article in journal (Refereed) Published
Abstract [en]

For the concept of aromaticity, energetic quantification is crucial. However, this has been elusive for excited-state (Baird) aromaticity. Here we report our serendipitous discovery of two nonplanar thiophene-fused chiral [4n]annulenes Th4COT Saddle and Th6CDH Screw, which by computational analysis turned out to be a pair of molecules suitable for energetic quantification of Baird aromaticity. Their enantiomers were separable chromatographically but racemized thermally, enabling investigation of the ring inversion kinetics. In contrast to Th6CDH Screw, which inverts through a nonplanar transition state, the inversion of Th4COT Saddle, progressing through a planar transition state, was remarkably accelerated upon photoexcitation. As predicted by Baird’s theory, the planar conformation of Th4COT Saddle is stabilized in the photoexcited state, thereby enabling lower activation enthalpy than that in the ground state. The lowering of the activation enthalpy, i.e., the energetic impact of excited-state aromaticity, was quantified experimentally to be as high as 21–22 kcal mol–1.

Place, publisher, year, edition, pages
2017. Vol. 8, 346
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Chemical Engineering
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URN: urn:nbn:se:uu:diva-333965DOI: 10.1038/s41467-017-00382-1ISI: 000408375700010OAI: oai:DiVA.org:uu-333965DiVA: diva2:1165383
Available from: 2017-12-13 Created: 2017-12-13 Last updated: 2017-12-13Bibliographically approved

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Jorner, KjellOttosson, Henrik

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