Wurster's blue-type cation radicals framed in a 5,10-Dihydrobenzo[a] indolo[2,3-c]carbazole (BIC) Skeleton

Dual electrochromism with drastic changes in UV/Vis/NIR and fluorescence

Takanori Suzuki, Yuto Sakano, Yusuke Tokimizu, Youhei Miura, Ryo Katoono, Kenshu Fujiwara, Naoki Yoshioka, Nobutaka Fujii, Hiroaki Ohno

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

Electron-donating dihydrobenzindolocarbazoles (BICs) 1 a-c, which adopt planar disk-shaped geometries, were prepared by gold(I)-catalyzed cyclization as a key step. Due to the presence of a 1,4-phenylenediamine (PD) moiety in the framework, they undergo reversible one-electron oxidation to the corresponding Wurster's Blue (WB)-type species that exhibits NIR absorptions up to λ=1200 nm. In the case of the N,N -dimethyl derivative, cation radical 1 c+. is stable enough to be isolated as a salt and X-ray analysis indicated paraquinoid-type bond alternation in the WB core unit, whereas the bond lengths in the peripheral benzene rings are identical to those in the neutral donor. Upon electrochemical interconversion, the redox pairs of 1 a-c and 1 a-c+. exhibited an electrochromic response in the UV/Vis/NIR region, which was accompanied by a drastic change in the fluorescence spectrum because only neutral donors 1 a-c are highly emissive (ΦF: 0.7-0.8). Potential for change: Both UV/Vis/NIR and fluorescence can be reversibly modified by application of electric potential to the highly fluorescent π-extended p-phenylenediamines with disk-shaped geometries to form stable cation radical species (see figure).

Original languageEnglish
Pages (from-to)1841-1846
Number of pages6
JournalChemistry - An Asian Journal
Volume9
Issue number7
DOIs
Publication statusPublished - 2014

Fingerprint

imidazole mustard
Tetramethylphenylenediamine
Electrochromism
Skeleton
Cations
Fluorescence
Electrons
Geometry
Cyclization
X ray analysis
Bond length
Benzene
Gold
Oxidation-Reduction
Salts
X-Rays
Derivatives
Oxidation
Electric potential
4-phenylenediamine

Keywords

  • fluorescence
  • gold
  • heterocycles
  • molecular response system
  • redox chemistry

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Wurster's blue-type cation radicals framed in a 5,10-Dihydrobenzo[a] indolo[2,3-c]carbazole (BIC) Skeleton : Dual electrochromism with drastic changes in UV/Vis/NIR and fluorescence. / Suzuki, Takanori; Sakano, Yuto; Tokimizu, Yusuke; Miura, Youhei; Katoono, Ryo; Fujiwara, Kenshu; Yoshioka, Naoki; Fujii, Nobutaka; Ohno, Hiroaki.

In: Chemistry - An Asian Journal, Vol. 9, No. 7, 2014, p. 1841-1846.

Research output: Contribution to journalArticle

Suzuki, Takanori ; Sakano, Yuto ; Tokimizu, Yusuke ; Miura, Youhei ; Katoono, Ryo ; Fujiwara, Kenshu ; Yoshioka, Naoki ; Fujii, Nobutaka ; Ohno, Hiroaki. / Wurster's blue-type cation radicals framed in a 5,10-Dihydrobenzo[a] indolo[2,3-c]carbazole (BIC) Skeleton : Dual electrochromism with drastic changes in UV/Vis/NIR and fluorescence. In: Chemistry - An Asian Journal. 2014 ; Vol. 9, No. 7. pp. 1841-1846.
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abstract = "Electron-donating dihydrobenzindolocarbazoles (BICs) 1 a-c, which adopt planar disk-shaped geometries, were prepared by gold(I)-catalyzed cyclization as a key step. Due to the presence of a 1,4-phenylenediamine (PD) moiety in the framework, they undergo reversible one-electron oxidation to the corresponding Wurster's Blue (WB)-type species that exhibits NIR absorptions up to λ=1200 nm. In the case of the N,N -dimethyl derivative, cation radical 1 c+. is stable enough to be isolated as a salt and X-ray analysis indicated paraquinoid-type bond alternation in the WB core unit, whereas the bond lengths in the peripheral benzene rings are identical to those in the neutral donor. Upon electrochemical interconversion, the redox pairs of 1 a-c and 1 a-c+. exhibited an electrochromic response in the UV/Vis/NIR region, which was accompanied by a drastic change in the fluorescence spectrum because only neutral donors 1 a-c are highly emissive (ΦF: 0.7-0.8). Potential for change: Both UV/Vis/NIR and fluorescence can be reversibly modified by application of electric potential to the highly fluorescent π-extended p-phenylenediamines with disk-shaped geometries to form stable cation radical species (see figure).",
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