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

doi:10.1002/anie.201611431

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

21 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 (T₁) by spectroscopic measurements and quantum calculations. The T₁ 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 T₁ 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 T₁ state. Furthermore, we show that the degree of structural smoothness affects the aromaticity reversal in the T₁ state.

Original language	English
Pages (from-to)	2932-2936
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	11
DOIs	https://doi.org/10.1002/anie.201611431
Publication status	Published - 2017 Mar 6

Bibliographical note

Funding Information:
The work at Yonsei University was supported by the Samsung Science and Technology Foundation (Project Number SSTF-BA1402-10). The quantum-chemical calculations were performed using the supercomputing resources of the Korea Institute of Science and Technology Information (KISTI). The work at Kyoto was supported by the JSPS (KAKENHI Grant Numbers 25220802 (Scientific Research (S)) and 26620081 (Exploratory Research)).

Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

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10.1002/anie.201611431

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

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 (T1) by spectroscopic measurements and quantum calculations. The T1 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 T1 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 T1 state. Furthermore, we show that the degree of structural smoothness affects the aromaticity reversal in the T1 state.",

author = "Yongseok Hong and Juwon Oh and Sung, {Young Mo} and Yasuo Tanaka and Atsuhiro Osuka and Dongho Kim",

note = "Funding Information: The work at Yonsei University was supported by the Samsung Science and Technology Foundation (Project Number SSTF-BA1402-10). The quantum-chemical calculations were performed using the supercomputing resources of the Korea Institute of Science and Technology Information (KISTI). The work at Kyoto was supported by the JSPS (KAKENHI Grant Numbers 25220802 (Scientific Research (S)) and 26620081 (Exploratory Research)). Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Oh, Juwon

AU - Sung, Young Mo

AU - Tanaka, Yasuo

AU - Osuka, Atsuhiro

AU - Kim, Dongho

N1 - Funding Information: The work at Yonsei University was supported by the Samsung Science and Technology Foundation (Project Number SSTF-BA1402-10). The quantum-chemical calculations were performed using the supercomputing resources of the Korea Institute of Science and Technology Information (KISTI). The work at Kyoto was supported by the JSPS (KAKENHI Grant Numbers 25220802 (Scientific Research (S)) and 26620081 (Exploratory Research)). Publisher Copyright: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2017/3/6

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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

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