7,7,8,8-tetraaryl-o-quinodimethane stabilized by dibenzo annulation: A helical π-electron system that exhibits electrochromic and unique chiroptical Properties

Takanori Suzuki, Yuto Sakano, Tomohiro Iwai, Shinichi Iwashita, Youhei Miura, Ryo Katoono, Hidetoshi Kawai, Kenshu Fujiwara, Yasushi Tsuji, Takanori Fukushima

Research output: Contribution to journalArticle

24 Citations (Scopus)

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 languageEnglish
Pages (from-to)117-123
Number of pages7
JournalChemistry - A European Journal
Volume19
Issue number1
DOIs
Publication statusPublished - 2013 Jan 2
Externally publishedYes

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Keywords

  • chirality
  • circular dichroism
  • electrochromism
  • helical structures
  • redox chemistry

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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