Electrochromic and unique chiroptical properties of helically deformed tetraarylquinodimethanes generated from less-hindered dicationic precursors upon reduction

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

2 Citations (Scopus)

Abstract

Electron-donating 1,1,4,4-tetraarylbutadiene is a representative electrochromic dye, and the same chromophore can be found in 9,10-bis(diarylmethylene)-9,10-dihydrophenanthrene (dibenzo-oQD) albeit in a fixed s-cis geometry. Unlike thermodynamically unstable 7,7,8,8-tetraaryl-o- quinodimethane, spontaneous electrocyclization is prohibited by dibenzo-annulation. Several derivatives of dibenzo-oQD were successfully generated despite highly strained geometry caused by steric hindrance between the bulky diarylmethylene units. Their precursors are phenanthrene-9,10-diyl bis(diarylmethylium) dyes (PDM2+) stabilized by four electron-donating alkoxy groups. The redox pairs of dibenzo-oQD/PDM2+ exhibit vivid change in color upon redox interconversion (electrochromism). Both dibenzo-oQD and PDM2+adopt a helical conformation, whose configuration is unstable. When a chiral alkoxy substituent is attached on each of the aryl groups, the point chirality is successfully transmitted to helicity of PDM2+. Resulting diastereomeric biasing is the key for dibenzo-oQD/PDM2+to exhibit the two-way-output response (e.g., UV-vis and CD). In addition, much more strained quinodimethane derivatives, 1,2-bis(diarylmethylene)acenaphthene and 1,16-diaryldibenzo[b,n]perylene, were also generated from the dicationic precursors, demonstrating that the reductive transformation can serve as a useful protocol to generate severely deformed π-conjugated systems.

Original languageEnglish
Pages (from-to)507-516
Number of pages10
JournalPure and Applied Chemistry
Volume86
Issue number4
DOIs
Publication statusPublished - 2014 Apr 17
Externally publishedYes

Fingerprint

Coloring Agents
Dyes
Perylene
Electrochromism
Derivatives
Geometry
Electrons
Chirality
Chromophores
Conformations
Color
Oxidation-Reduction
alkoxyl radical
Haemophilus influenzae type b-polysaccharide vaccine-diphtheria toxoid conjugate
phenanthrene
acenaphthene

Keywords

  • Chirality
  • Dication
  • Dye
  • Electrochiroptics
  • Electrochromism
  • ISNA-15
  • Redox system
  • Strained molecules

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Electrochromic and unique chiroptical properties of helically deformed tetraarylquinodimethanes generated from less-hindered dicationic precursors upon reduction. / Suzuki, Takanori; Sakano, Yuto; Iwai, Tomohiro; Iwashita, Shinichi; Miura, Youhei; Katoono, Ryo; Kawai, Hidetoshi; Fujiwara, Kenshu; Tsuji, Yasushi; Fukushima, Takanori.

In: Pure and Applied Chemistry, Vol. 86, No. 4, 17.04.2014, p. 507-516.

Research output: Contribution to journalArticle

Suzuki, Takanori ; Sakano, Yuto ; Iwai, Tomohiro ; Iwashita, Shinichi ; Miura, Youhei ; Katoono, Ryo ; Kawai, Hidetoshi ; Fujiwara, Kenshu ; Tsuji, Yasushi ; Fukushima, Takanori. / Electrochromic and unique chiroptical properties of helically deformed tetraarylquinodimethanes generated from less-hindered dicationic precursors upon reduction. In: Pure and Applied Chemistry. 2014 ; Vol. 86, No. 4. pp. 507-516.
@article{26befd22aa4f4246a117e1327ee22fd8,
title = "Electrochromic and unique chiroptical properties of helically deformed tetraarylquinodimethanes generated from less-hindered dicationic precursors upon reduction",
abstract = "Electron-donating 1,1,4,4-tetraarylbutadiene is a representative electrochromic dye, and the same chromophore can be found in 9,10-bis(diarylmethylene)-9,10-dihydrophenanthrene (dibenzo-oQD) albeit in a fixed s-cis geometry. Unlike thermodynamically unstable 7,7,8,8-tetraaryl-o- quinodimethane, spontaneous electrocyclization is prohibited by dibenzo-annulation. Several derivatives of dibenzo-oQD were successfully generated despite highly strained geometry caused by steric hindrance between the bulky diarylmethylene units. Their precursors are phenanthrene-9,10-diyl bis(diarylmethylium) dyes (PDM2+) stabilized by four electron-donating alkoxy groups. The redox pairs of dibenzo-oQD/PDM2+ exhibit vivid change in color upon redox interconversion (electrochromism). Both dibenzo-oQD and PDM2+adopt a helical conformation, whose configuration is unstable. When a chiral alkoxy substituent is attached on each of the aryl groups, the point chirality is successfully transmitted to helicity of PDM2+. Resulting diastereomeric biasing is the key for dibenzo-oQD/PDM2+to exhibit the two-way-output response (e.g., UV-vis and CD). In addition, much more strained quinodimethane derivatives, 1,2-bis(diarylmethylene)acenaphthene and 1,16-diaryldibenzo[b,n]perylene, were also generated from the dicationic precursors, demonstrating that the reductive transformation can serve as a useful protocol to generate severely deformed π-conjugated systems.",
keywords = "Chirality, Dication, Dye, Electrochiroptics, Electrochromism, ISNA-15, Redox system, Strained molecules",
author = "Takanori Suzuki and Yuto Sakano and Tomohiro Iwai and Shinichi Iwashita and Youhei Miura and Ryo Katoono and Hidetoshi Kawai and Kenshu Fujiwara and Yasushi Tsuji and Takanori Fukushima",
year = "2014",
month = "4",
day = "17",
doi = "10.1515/pac-2013-1003",
language = "English",
volume = "86",
pages = "507--516",
journal = "Pure and Applied Chemistry",
issn = "0033-4545",
publisher = "IUPAC Secretariat",
number = "4",

}

TY - JOUR

T1 - Electrochromic and unique chiroptical properties of helically deformed tetraarylquinodimethanes generated from less-hindered dicationic precursors upon reduction

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 - 2014/4/17

Y1 - 2014/4/17

N2 - Electron-donating 1,1,4,4-tetraarylbutadiene is a representative electrochromic dye, and the same chromophore can be found in 9,10-bis(diarylmethylene)-9,10-dihydrophenanthrene (dibenzo-oQD) albeit in a fixed s-cis geometry. Unlike thermodynamically unstable 7,7,8,8-tetraaryl-o- quinodimethane, spontaneous electrocyclization is prohibited by dibenzo-annulation. Several derivatives of dibenzo-oQD were successfully generated despite highly strained geometry caused by steric hindrance between the bulky diarylmethylene units. Their precursors are phenanthrene-9,10-diyl bis(diarylmethylium) dyes (PDM2+) stabilized by four electron-donating alkoxy groups. The redox pairs of dibenzo-oQD/PDM2+ exhibit vivid change in color upon redox interconversion (electrochromism). Both dibenzo-oQD and PDM2+adopt a helical conformation, whose configuration is unstable. When a chiral alkoxy substituent is attached on each of the aryl groups, the point chirality is successfully transmitted to helicity of PDM2+. Resulting diastereomeric biasing is the key for dibenzo-oQD/PDM2+to exhibit the two-way-output response (e.g., UV-vis and CD). In addition, much more strained quinodimethane derivatives, 1,2-bis(diarylmethylene)acenaphthene and 1,16-diaryldibenzo[b,n]perylene, were also generated from the dicationic precursors, demonstrating that the reductive transformation can serve as a useful protocol to generate severely deformed π-conjugated systems.

AB - Electron-donating 1,1,4,4-tetraarylbutadiene is a representative electrochromic dye, and the same chromophore can be found in 9,10-bis(diarylmethylene)-9,10-dihydrophenanthrene (dibenzo-oQD) albeit in a fixed s-cis geometry. Unlike thermodynamically unstable 7,7,8,8-tetraaryl-o- quinodimethane, spontaneous electrocyclization is prohibited by dibenzo-annulation. Several derivatives of dibenzo-oQD were successfully generated despite highly strained geometry caused by steric hindrance between the bulky diarylmethylene units. Their precursors are phenanthrene-9,10-diyl bis(diarylmethylium) dyes (PDM2+) stabilized by four electron-donating alkoxy groups. The redox pairs of dibenzo-oQD/PDM2+ exhibit vivid change in color upon redox interconversion (electrochromism). Both dibenzo-oQD and PDM2+adopt a helical conformation, whose configuration is unstable. When a chiral alkoxy substituent is attached on each of the aryl groups, the point chirality is successfully transmitted to helicity of PDM2+. Resulting diastereomeric biasing is the key for dibenzo-oQD/PDM2+to exhibit the two-way-output response (e.g., UV-vis and CD). In addition, much more strained quinodimethane derivatives, 1,2-bis(diarylmethylene)acenaphthene and 1,16-diaryldibenzo[b,n]perylene, were also generated from the dicationic precursors, demonstrating that the reductive transformation can serve as a useful protocol to generate severely deformed π-conjugated systems.

KW - Chirality

KW - Dication

KW - Dye

KW - Electrochiroptics

KW - Electrochromism

KW - ISNA-15

KW - Redox system

KW - Strained molecules

UR - http://www.scopus.com/inward/record.url?scp=84899865017&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84899865017&partnerID=8YFLogxK

U2 - 10.1515/pac-2013-1003

DO - 10.1515/pac-2013-1003

M3 - Article

AN - SCOPUS:84899865017

VL - 86

SP - 507

EP - 516

JO - Pure and Applied Chemistry

JF - Pure and Applied Chemistry

SN - 0033-4545

IS - 4

ER -