Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 1867-1873 |
| Number of pages | 7 |
| Journal | Bulletin of the Chemical Society of Japan |
| Volume | 92 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - Jan 1 2019 |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
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An azulene-based chiral helicene and its air-stable cation radical. / Narita, Masahiro; Teraoka, Takaaki; Murafuji, Toshihiro; Shiota, Yoshihito; Yoshizawa, Kazunari; Mori, Shigeki; Uno, Hidemitsu; Kanegawa, Shinji; Sato, Osamu; Goto, Kenta; Tani, Fumito.
In: Bulletin of the Chemical Society of Japan, Vol. 92, No. 11, 01.01.2019, p. 1867-1873.Research output: Contribution to journal › Article
}
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
PY - 2019/1/1
Y1 - 2019/1/1
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.
UR - http://www.scopus.com/inward/record.url?scp=85074497914&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85074497914&partnerID=8YFLogxK
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 -