Synthetic routes to polyheteroacenes

Characterization of a heterocyclic ladder polymer containing phenoxathiinium-type building blocks

Kenichi Oyaizu, Takefumi Mikami, Fumio Mitsuhashi, Eishun Tsuchida

    Research output: Contribution to journalArticle

    36 Citations (Scopus)

    Abstract

    The synthetic routes to ladder polymers that consist of benzenetetrayl subunits with oxo and methylsulfonio linkages are described. As the key intermediate, poly(phenylene oxide)s having pendant methylsulfenyl groups are prepared by copper-catalyzed oxidative polymerization of the corresponding phenols with O2. The oxidation of the polymer with an equimolar amount of H2O2 in the presence of acetic acid effects the high-yielding conversion of methylsulfenyl to methylsulfinyl groups without the formation of the undesired methylsulfonyl groups. The superacidified condensation of the resulting polymer (Swern reaction of aryl sulfoxides) under dilution conditions induces the polymer-analogous intramolecular electrophilic ring-closing reaction of the hydroxymethylphenylsulfonium cation onto the adjacent benzene ring to yield the required ladder polymer, which has proved to be a semiconductor with an intrinsic electric conductivity of 2 × 10-5 S/cm. A comparison of the spectroscopic properties of the ladder polymer with those of the model compounds such as 5-methylphenoxathiinium triflate and phenoxathiin discloses π-electron delocalization over the methylsulfonio linkages, demonstrating the efficacy of the ladderization for p-π/d-π interactions in arylsulfonium moieties. This synthetic approach permits the thio and alkylsulfonio ladder linkages for a variety of phenyl ethers to form in high yields.

    Original languageEnglish
    Pages (from-to)67-78
    Number of pages12
    JournalMacromolecules
    Volume35
    Issue number1
    DOIs
    Publication statusPublished - 2002 Jan 1

    Fingerprint

    Ladders
    Polymers
    Phenyl Ethers
    Sulfoxides
    Phenols
    Benzene
    Acetic acid
    Acetic Acid
    Oxides
    Dilution
    Cations
    Copper
    Condensation
    Ethers
    Positive ions
    Polymerization
    Semiconductor materials
    Oxidation
    Electrons

    ASJC Scopus subject areas

    • Materials Chemistry

    Cite this

    Synthetic routes to polyheteroacenes : Characterization of a heterocyclic ladder polymer containing phenoxathiinium-type building blocks. / Oyaizu, Kenichi; Mikami, Takefumi; Mitsuhashi, Fumio; Tsuchida, Eishun.

    In: Macromolecules, Vol. 35, No. 1, 01.01.2002, p. 67-78.

    Research output: Contribution to journalArticle

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