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
N1 - Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
PY - 2017/3/6
Y1 - 2017/3/6
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 (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.
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 (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.
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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 -