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 language | English |
|---|---|
| Pages (from-to) | 2932-2936 |
| Number of pages | 5 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 56 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - 2017 Jan 1 |
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All Science Journal Classification (ASJC) codes
- Catalysis
- Chemistry(all)
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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 journal › Article
TY - JOUR
T1 - The Extension of Baird's Rule to Twisted Heteroannulenes
T2 - Aromaticity Reversal of Singly and Doubly Twisted Molecular Systems in the Lowest Triplet State
AU - Hong, Yongseok
AU - Oh, Juwon
AU - Sung, Young Mo
AU - Tanaka, Yasuo
AU - Osuka, Atsuhiro
AU - Kim, Dongho
PY - 2017/1/1
Y1 - 2017/1/1
N2 - 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.
AB - 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.
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UR - http://www.scopus.com/inward/citedby.url?scp=85012031652&partnerID=8YFLogxK
U2 - 10.1002/anie.201611431
DO - 10.1002/anie.201611431
M3 - Article
C2 - 28165184
AN - SCOPUS:85012031652
VL - 56
SP - 2932
EP - 2936
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 11
ER -