The Extension of Baird's Rule to Twisted Heteroannulenes: Aromaticity Reversal of Singly and Doubly Twisted Molecular Systems in the Lowest Triplet State

Yongseok Hong, Juwon Oh, Young Mo Sung, Yasuo Tanaka, Atsuhiro Osuka, Dongho Kim

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

We have investigated the aromaticity of singly twisted Möbius aromatic and doubly twisted Hückel antiaromatic bis(palladium(II)) [36]octaphyrins in the lowest triplet state (T 1 ) by spectroscopic measurements and quantum calculations. The T 1 state of the singly twisted Möbius [36]octaphyrin shows broad and weak absorption spectral features that are analogous to those of antiaromatic expanded porphyrins while the T 1 state of the doubly twisted Hückel [36]octaphyrin exhibits intense and distinct spectral features, indicating the aromatic nature. These results along with theoretical calculations support the hypothesis that the aromaticity is reversed in the T 1 state. Furthermore, we show that the degree of structural smoothness affects the aromaticity reversal in the T 1 state.

Original languageEnglish
Pages (from-to)2932-2936
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number11
DOIs
Publication statusPublished - 2017 Jan 1

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Porphyrins
Palladium

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

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abstract = "We have investigated the aromaticity of singly twisted M{\"o}bius aromatic and doubly twisted H{\"u}ckel antiaromatic bis(palladium(II)) [36]octaphyrins in the lowest triplet state (T 1 ) by spectroscopic measurements and quantum calculations. The T 1 state of the singly twisted M{\"o}bius [36]octaphyrin shows broad and weak absorption spectral features that are analogous to those of antiaromatic expanded porphyrins while the T 1 state of the doubly twisted H{\"u}ckel [36]octaphyrin exhibits intense and distinct spectral features, indicating the aromatic nature. These results along with theoretical calculations support the hypothesis that the aromaticity is reversed in the T 1 state. Furthermore, we show that the degree of structural smoothness affects the aromaticity reversal in the T 1 state.",
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The Extension of Baird's Rule to Twisted Heteroannulenes : Aromaticity Reversal of Singly and Doubly Twisted Molecular Systems in the Lowest Triplet State. / Hong, Yongseok; Oh, Juwon; Sung, Young Mo; Tanaka, Yasuo; Osuka, Atsuhiro; Kim, Dongho.

In: Angewandte Chemie - International Edition, Vol. 56, No. 11, 01.01.2017, p. 2932-2936.

Research output: Contribution to journalArticle

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