TY - JOUR
T1 - An azulene-based chiral helicene and its air-stable cation radical
AU - Narita, Masahiro
AU - Teraoka, Takaaki
AU - Murafuji, Toshihiro
AU - Shiota, Yoshihito
AU - Yoshizawa, Kazunari
AU - Mori, Shigeki
AU - Uno, Hidemitsu
AU - Kanegawa, Shinji
AU - Sato, Osamu
AU - Goto, Kenta
AU - Tani, Fumito
N1 - Funding Information:
This work was supported by Grant-in-Aid for JSPS KAKENHI Grant No. JP18K05087 (F. T.) and the Cooperative Research Program ?Network Joint Research Center for Materials and Devices (Institute for Materials Chemistry and Engineering, Kyushu University)?. The authors thank Prof. H. Furuta and Dr. M. Ishida of Kyushu University for their generous permission to use the HPLC instrument, Prof. S. Suzuki of Osaka University and Dr. T. Koide of Kyushu University for their helpful advice about ESR spectral analysis, Prof. Y. Shimazaki for his valuable suggestions about the chemical oxidation and Mr. T. Matsumoto of Kyushu University for his kind assistance to use the X-ray crystallography facility.
Funding Information:
This work was supported by Grant-in-Aid for JSPS KAKENHI Grant No. JP18K05087 (F. T.) and the Cooperative Research Program “Network Joint Research Center for Materials and Devices (Institute for Materials Chemistry and Engineering, Kyushu University)”. The authors thank Prof. H. Furuta and Dr. M. Ishida of Kyushu University for their generous permission to use the HPLC instrument, Prof. S. Suzuki of Osaka University and Dr. T. Koide of Kyushu University for their helpful advice about ESR spectral analysis, Prof. Y. Shimazaki for his valuable suggestions about the chemical oxidation and Mr. T. Matsumoto of Kyushu University for his kind assistance to use the X-ray crystallography facility.
Publisher Copyright:
© 2019 The Chemical Society of Japan.
PY - 2019
Y1 - 2019
N2 - A helicene compound called AIBTh, wherein two azulene units are fused with isobenzothiophene, has been prepared and characterized by spectroscopic and crystallographic methods. The enantiomers of AIBTh were resolved by HPLC, exhibiting stable optical activity. AIBTh showed two reversible oxidation and one irreversible reduction waves with a HOMO-LUMO gap of 2.07 eV. Upon one-electron oxidation of AIBTh, its air-stable cation radical was isolated and analyzed by EPR as well as X-ray crystallography. Based on the EPR spectrum, the crystal structure, and DFT calculation, it is suggested that favorable resonance structures including aromatic tropylium cation forms and wide delocalization of electronic spin are dominating in the electronic structure of the cation radical.
AB - A helicene compound called AIBTh, wherein two azulene units are fused with isobenzothiophene, has been prepared and characterized by spectroscopic and crystallographic methods. The enantiomers of AIBTh were resolved by HPLC, exhibiting stable optical activity. AIBTh showed two reversible oxidation and one irreversible reduction waves with a HOMO-LUMO gap of 2.07 eV. Upon one-electron oxidation of AIBTh, its air-stable cation radical was isolated and analyzed by EPR as well as X-ray crystallography. Based on the EPR spectrum, the crystal structure, and DFT calculation, it is suggested that favorable resonance structures including aromatic tropylium cation forms and wide delocalization of electronic spin are dominating in the electronic structure of the cation radical.
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U2 - 10.1246/bcsj.20190219
DO - 10.1246/bcsj.20190219
M3 - Article
AN - SCOPUS:85074497914
VL - 92
SP - 1867
EP - 1873
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 11
ER -