Energetics of Baird aromaticity supported by inversion of photoexcited chiral [4n]annulene derivatives

Michihisa Ueda, Kjell Jorner, Young Mo Sung, Tadashi Mori, Qi Xiao, Dongho Kim, Henrik Ottosson, Takuzo Aida, Yoshimitsu Itoh

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

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 Th4 COT Saddle and Th6 CDH 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 Th6 CDH Screw, which inverts through a nonplanar transition state, the inversion of Th4 COT Saddle, progressing through a planar transition state, was remarkably accelerated upon photoexcitation. As predicted by Baird's theory, the planar conformation of Th4 COT 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.

Original languageEnglish
Article number346
JournalNature Communications
Volume8
Issue number1
DOIs
Publication statusPublished - 2017 Aug 4

Fingerprint

Thiophenes
saddles
Excited states
Enthalpy
Chemical activation
screws
inversions
Derivatives
Enantiomers
Photoexcitation
enthalpy
activation
Ground state
Conformations
enantiomers
thiophenes
photoexcitation
Molecules
Kinetics
excitation

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

Cite this

Ueda, Michihisa ; Jorner, Kjell ; Sung, Young Mo ; Mori, Tadashi ; Xiao, Qi ; Kim, Dongho ; Ottosson, Henrik ; Aida, Takuzo ; Itoh, Yoshimitsu. / Energetics of Baird aromaticity supported by inversion of photoexcited chiral [4n]annulene derivatives. In: Nature Communications. 2017 ; Vol. 8, No. 1.
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Energetics of Baird aromaticity supported by inversion of photoexcited chiral [4n]annulene derivatives. / Ueda, Michihisa; Jorner, Kjell; Sung, Young Mo; Mori, Tadashi; Xiao, Qi; Kim, Dongho; Ottosson, Henrik; Aida, Takuzo; Itoh, Yoshimitsu.

In: Nature Communications, Vol. 8, No. 1, 346, 04.08.2017.

Research output: Contribution to journalArticle

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