Preparation and electrochemical and optical properties of unsymmetrically substituted phthalocyanines with one or two trithiole rings and related symmetric derivatives

Takeshi Kimura, Nagisa Kanota, Kenji Matsui, Ichiro Tanaka, Takaaki Tsuboi, Yutaka Takaguchi, Akinori Yomogita, Takatsugu Wakahara, Shunsuke Kuwahara, Fumi Nagatsugi, Takeshi Akasaka

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Abstract

4,5-Bis(benzylthio)-3,6-diethylphthalonitrile (1) was mixed with 4-t-butylphthalonitrile and then treated with lithium alkoxide in n-hexanol to produce the corresponding unsymmetrically substituted phthalocyanines (2) and (3) with two or four benzylthio groups, respectively. Treatment of phthalocyanine (2) with nickel(II) acetate yielded the corresponding metal complex 2-Ni. Two benzyl groups of 2 and 2-Ni were removed with lithium/THF/ammonia at -78°C under argon, and the dithiolate anions generated were then reacted with elemental sulfur to give monotrithiolophthalocyanines (5) and (5-Ni). A similar treatment of 3 produced bistrithiolophthalocyanine (6). Tetrakistrithiolophthalocyanine (7-Ni) was prepared by complexation of phthalocyanine (4) with nickel(II) acetate, followed by a Birch reduction of the resulting nickel(II) complex (4-Ni), and then sulfurization and cyclization of the octathiolate anions that were generated. The structures of the phthalocyanines were determined by 1H NMR and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. The optical and electrochemical properties of the phthalocyanines were examined by UV-vis absorption spectroscopy and cyclic voltammetry. Treatment of 5, 5-Ni, 6, 7, and 7-Ni with trifluoroacetic acid in chloroform generated positively charged species, which were characterized by UV-vis and/or NMR spectroscopy.

Original languageEnglish
Pages (from-to)3577-3583
Number of pages7
JournalInorganic chemistry
Volume47
Issue number9
DOIs
Publication statusPublished - 2008 May 5

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Kimura, T., Kanota, N., Matsui, K., Tanaka, I., Tsuboi, T., Takaguchi, Y., Yomogita, A., Wakahara, T., Kuwahara, S., Nagatsugi, F., & Akasaka, T. (2008). Preparation and electrochemical and optical properties of unsymmetrically substituted phthalocyanines with one or two trithiole rings and related symmetric derivatives. Inorganic chemistry, 47(9), 3577-3583. https://doi.org/10.1021/ic701841j