Abstract
When two benzene rings are fused to a tetraaryl-o-quinodimethane skeleton, sterically hindered helical molecules 1 acquire a high thermodynamic stability. Because the tetraarylbutadiene subunit contains electron-donating alkoxy groups, 1 undergo reversible two-electron oxidation to 22+, which can be isolated as deeply colored stable salts. Intramolecular transfer of the point chirality (e.g., sec-butyl) on the aryl groups to helicity induces a diastereomeric preference in dications 2 b2+ and 2 c2+, which represents an efficient method for enhancing circular-dichroism signals. Thus, those redox pairs can serve as new electrochiroptical response systems. X-ray analysis of dication 22+ revealed π-π stacking interaction of the diarylmethylium moieties, which is also present in solution. The stacking geometry is the key contributor to the chirosolvatochromic response.
| Original language | English |
|---|---|
| Pages (from-to) | 117-123 |
| Number of pages | 7 |
| Journal | Chemistry - A European Journal |
| Volume | 19 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 2013 Jan 2 |
| Externally published | Yes |
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Keywords
- chirality
- circular dichroism
- electrochromism
- helical structures
- redox chemistry
ASJC Scopus subject areas
- Chemistry(all)
Cite this
7,7,8,8-tetraaryl-o-quinodimethane stabilized by dibenzo annulation : A helical π-electron system that exhibits electrochromic and unique chiroptical Properties. / Suzuki, Takanori; Sakano, Yuto; Iwai, Tomohiro; Iwashita, Shinichi; Miura, Youhei; Katoono, Ryo; Kawai, Hidetoshi; Fujiwara, Kenshu; Tsuji, Yasushi; Fukushima, Takanori.
In: Chemistry - A European Journal, Vol. 19, No. 1, 02.01.2013, p. 117-123.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - 7,7,8,8-tetraaryl-o-quinodimethane stabilized by dibenzo annulation
T2 - A helical π-electron system that exhibits electrochromic and unique chiroptical Properties
AU - Suzuki, Takanori
AU - Sakano, Yuto
AU - Iwai, Tomohiro
AU - Iwashita, Shinichi
AU - Miura, Youhei
AU - Katoono, Ryo
AU - Kawai, Hidetoshi
AU - Fujiwara, Kenshu
AU - Tsuji, Yasushi
AU - Fukushima, Takanori
PY - 2013/1/2
Y1 - 2013/1/2
N2 - When two benzene rings are fused to a tetraaryl-o-quinodimethane skeleton, sterically hindered helical molecules 1 acquire a high thermodynamic stability. Because the tetraarylbutadiene subunit contains electron-donating alkoxy groups, 1 undergo reversible two-electron oxidation to 22+, which can be isolated as deeply colored stable salts. Intramolecular transfer of the point chirality (e.g., sec-butyl) on the aryl groups to helicity induces a diastereomeric preference in dications 2 b2+ and 2 c2+, which represents an efficient method for enhancing circular-dichroism signals. Thus, those redox pairs can serve as new electrochiroptical response systems. X-ray analysis of dication 22+ revealed π-π stacking interaction of the diarylmethylium moieties, which is also present in solution. The stacking geometry is the key contributor to the chirosolvatochromic response.
AB - When two benzene rings are fused to a tetraaryl-o-quinodimethane skeleton, sterically hindered helical molecules 1 acquire a high thermodynamic stability. Because the tetraarylbutadiene subunit contains electron-donating alkoxy groups, 1 undergo reversible two-electron oxidation to 22+, which can be isolated as deeply colored stable salts. Intramolecular transfer of the point chirality (e.g., sec-butyl) on the aryl groups to helicity induces a diastereomeric preference in dications 2 b2+ and 2 c2+, which represents an efficient method for enhancing circular-dichroism signals. Thus, those redox pairs can serve as new electrochiroptical response systems. X-ray analysis of dication 22+ revealed π-π stacking interaction of the diarylmethylium moieties, which is also present in solution. The stacking geometry is the key contributor to the chirosolvatochromic response.
KW - chirality
KW - circular dichroism
KW - electrochromism
KW - helical structures
KW - redox chemistry
UR - http://www.scopus.com/inward/record.url?scp=84871556696&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84871556696&partnerID=8YFLogxK
U2 - 10.1002/chem.201203092
DO - 10.1002/chem.201203092
M3 - Article
C2 - 23169568
AN - SCOPUS:84871556696
VL - 19
SP - 117
EP - 123
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 1
ER -