Development of Organic Conductors with Self-Assembled Architectures of Biomolecules: Synthesis and Crystal Structures of Nucleobase-Functionalized Tetrathiafulvalene Derivatives

• Tsuyoshi Murata

  Department of Chemistry, Graduate School of Science, Osaka University

• Eigo Miyazaki

  Department of Chemistry, Graduate School of Science, Osaka University

• Suguru Maki

  Department of Chemistry, Graduate School of Science, Osaka University

• Yoshikazu Umemoto

  Department of Chemistry, Graduate School of Science, Osaka University

• Makoto Ohmoto

  Department of Chemistry, Graduate School of Science, Osaka University

• Kazuhiro Nakasuji

  Department of Chemistry, Graduate School of Science, Osaka University

• Yasushi Morita

  Department of Chemistry, Graduate School of Science, Osaka University

抄録

Supramolecular assemblies and charge-transfer complexes of new nucleobase-functionalized tetrathiafulvalene (TTF) derivatives were investigated. Stille-type cross-coupling reaction between tributylstannylated TTF and iodinated nucleobase derivatives yielded mono- and bisnucleobase-substituted TTF derivatives. The electrochemical measurements revealed that the uracil- and cytosine-substituted derivatives possessed strong electron-donating abilities comparable to that of pristine TTF, and the electron-deficient features of adenine and guanine caused high potential shifts of the oxidation waves. In the solution-state electronic spectra, the intramolecular charge-transfer absorption bands were observed at a low-energy region. In the crystal structures, the donor molecules constructed supramolecular polymers by the complementary hydrogen-bonds inherent in nucleobases; a one-dimensional zigzag chain in the adenine-substituted derivative and a linear chain in the bis(uracil)-substituted derivative. The tetracyanoquinodimethane complexes of uracil- and cytosine-substituted derivatives possessed a mixed valence state exhibiting high conductivities (room-temperature conductivities = 10−2–10−1 S cm−1). In the cyananilic acid complexes, cytosine- and adenine-substituted TTF acted as electron-donors and proton-acceptors to yield simultaneous charge- and proton-transfer complexes.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 85 (9), 995-1006, 2012-09

  Oxford University Press (OUP)

キーワード

• General Chemistry

詳細情報

• CRID: 1360846644026994304
• NII論文ID: 130004153120
• DOI: 10.1246/bcsj.20120102
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/85/9/995/56274263/bcsj.20120102.pdf
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