Preparation and electrochemical properties of 1,4,8,11,15,18,22,25- octalkylphthalocyanines containing four trithiole rings

Takeshi Kimura, Takahiro Suzuki, Yutaka Takaguchi, Akinori Yomogita, Takatsugu Wakahara, Takeshi Akasaka

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

1,4,8,11,15,18,22,25-Octalkyl-2,3;9,10;16,17;23,24-tetrakis(o- xylylenedithio)phthalocyanines 4a-d (alkyl = ethyl, butyl, octyl, and dodecyl) were prepared in moderate yields by treatment of 3,6-dialkyl-4,5-(o- xylylenedithio)phthalonitriles 3a-d with lithium in n-pentanol. Reductive removal of the four o-xylylene groups from 4b and 4c was performed with lithium/THF/ammonia, and the octathiolate anions generated were then treated with elemental sulfur to give the new phthalocyanines 6b and 6c, respectively, each containing four trithiole rings, after partial desulfurization and ring-contraction reactions of the corresponding phthalocyanines 5b and 5c. The structures of the phthalocyanines were determined by 1H NMR spectroscopy and MALDI-TOF mass spectrometry. The absorptions of the Q-bands of 4a-d were observed at λmax ≈ 770 nm in their UV/Vis spectra, while those of 4b-Ni, 5b, 5c, and 6c were found in a region, blue-shifted relative to 4a-d. When the UV/Vis spectrum of 6c was measured in concentrated sulfuric acid, the λmax value of its Q-band was 887 nm (log ε = 4.5), which suggests that the positive charge generated on 6c strongly affects the π-conjugation of the phthalocyanine skeleton. The ESR spectrum was observed as one broadening signal on treatment of 6c with SbCl5. The redox potentials of the phthalocyanines were determined by cyclic voltammetry.

Original languageEnglish
Pages (from-to)1262-1270
Number of pages9
JournalEuropean Journal of Organic Chemistry
Issue number5
DOIs
Publication statusPublished - Feb 27 2006

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Electrochemical properties
preparation
rings
lithium
sulfuric acid
conjugation
musculoskeletal system
Lithium
contraction
ammonia
sulfur
mass spectroscopy
anions
nuclear magnetic resonance
Desulfurization
Ammonia
Sulfur
spectroscopy
Nuclear magnetic resonance spectroscopy
Cyclic voltammetry

Keywords

  • Phthalocyanines
  • Radical ions
  • Sulfur heterocycles

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Preparation and electrochemical properties of 1,4,8,11,15,18,22,25- octalkylphthalocyanines containing four trithiole rings. / Kimura, Takeshi; Suzuki, Takahiro; Takaguchi, Yutaka; Yomogita, Akinori; Wakahara, Takatsugu; Akasaka, Takeshi.

In: European Journal of Organic Chemistry, No. 5, 27.02.2006, p. 1262-1270.

Research output: Contribution to journalArticle

Kimura, Takeshi ; Suzuki, Takahiro ; Takaguchi, Yutaka ; Yomogita, Akinori ; Wakahara, Takatsugu ; Akasaka, Takeshi. / Preparation and electrochemical properties of 1,4,8,11,15,18,22,25- octalkylphthalocyanines containing four trithiole rings. In: European Journal of Organic Chemistry. 2006 ; No. 5. pp. 1262-1270.
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AB - 1,4,8,11,15,18,22,25-Octalkyl-2,3;9,10;16,17;23,24-tetrakis(o- xylylenedithio)phthalocyanines 4a-d (alkyl = ethyl, butyl, octyl, and dodecyl) were prepared in moderate yields by treatment of 3,6-dialkyl-4,5-(o- xylylenedithio)phthalonitriles 3a-d with lithium in n-pentanol. Reductive removal of the four o-xylylene groups from 4b and 4c was performed with lithium/THF/ammonia, and the octathiolate anions generated were then treated with elemental sulfur to give the new phthalocyanines 6b and 6c, respectively, each containing four trithiole rings, after partial desulfurization and ring-contraction reactions of the corresponding phthalocyanines 5b and 5c. The structures of the phthalocyanines were determined by 1H NMR spectroscopy and MALDI-TOF mass spectrometry. The absorptions of the Q-bands of 4a-d were observed at λmax ≈ 770 nm in their UV/Vis spectra, while those of 4b-Ni, 5b, 5c, and 6c were found in a region, blue-shifted relative to 4a-d. When the UV/Vis spectrum of 6c was measured in concentrated sulfuric acid, the λmax value of its Q-band was 887 nm (log ε = 4.5), which suggests that the positive charge generated on 6c strongly affects the π-conjugation of the phthalocyanine skeleton. The ESR spectrum was observed as one broadening signal on treatment of 6c with SbCl5. The redox potentials of the phthalocyanines were determined by cyclic voltammetry.

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