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2004 Fiscal Year Final Research Report Summary

Suplamolecules with Fine Controlled Metal Assembly for a New Catalyst based on Multi-electron Transfer

Research Project

Project/Area Number 15350073
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Polymer chemistry
Research InstitutionKeio University

Principal Investigator

YAMAMOTO Kimihisa  Keio University, Faculty of Science and Technology, Professor, 理工学部, 教授 (80220458)

Co-Investigator(Kenkyū-buntansha) HIGUCHI Masayoshi  National Institute for Materials Science, Advanced Materials Laboratory, Senior Researcher, 物質研究所, 主任研究員 (80306852)
Project Period (FY) 2003 – 2004
KeywordsPhenylazomthine / dendrimer / Nao-catalyst / Metal assembling / π-conjugation / Organic-metalhybrid
Research Abstract

The radial stepwise complexation was also observed for the other dendrimers with phenylazomethine dendron skeletons. With all dendrimers, a four-step shift of the isosbestic point was observed with gradual addition of stannous chloride. In DPA G4 with a triphenylamine core, the shifts occur after the addition of 3, 6, 12, and 24 equivalents of SnCl_2. In DPA with a porphyrine core, the shifts occur after the addition of 4, 8, 16, and 32 equivalents. In the aniline-capped DPA G4 dendron, the shifts occur after the addition of 1, 2, 4, and 8 equivalents. In each dendrimer, the amounts of SnCl_2 added to the solution agree with the number of imines in the 1^<st> to 4^<th> shells. These results support that the complexation in DPA derivatives proceeds from the core imines to the terminal ones. The basicity of the inner imines is enhanced by the electron-releasing effect of the outer imines, and the stepwise complexation is caused by the different basicity of the imines between the shells. This complexation behavior means that the number and the position of the metal ions in the dendrimers are controllable.
During the complexation of DPA-F G2 with SnCl_2, two shifts in the isosbestic point appeared on adding 0-4 and 5-6 equivalents of SnCl_2 in the UV-vis spectra. This result shows that the imines present in the 2^<nd> shell were complexed first and then those present in the 1^<st> shell, whose basicity was lowered by the electron-withdrawing group. On adding SnCl_2 to DPA-F G3, three shifts of the isosbestic point appeared upon adding 0-4, 5-12, and 13-14 equivalents of SnCL_2. That is, the imines present in the 2^<nd> shell were complexed first, then those present in the 3^<rd> shell, and finally those present in the 1^<st> shell.

  • Research Products

    (12 results)

All 2004 2003

All Journal Article (12 results)

  • [Journal Article] Fine Control of the Release and Encapsulation of Fe Ions in Dendrimers through Ferritin-like Redox Switching2004

    • Author(s)
      Yamamoto et al.
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 1630-1631

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Novel Poly(p-phenylene vinylene)s with a Phenylazomethine Dendron as a Metal-Collecting2004

    • Author(s)
      Yamamoto et al.
    • Journal Title

      Organic Letters. 6

      Pages: 1179-1182

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of Asymmetrically Arranged Dendrimers with a Carbazole Dendron and a Phenylazomethine Dendron2004

    • Author(s)
      Yamamoto et al.
    • Journal Title

      Macromolecules 37

      Pages: 5531-5537

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Fine Control of the Release and Encapsulation of Fe Ions in Dendrimers through Ferritin-like Redox Switching2004

    • Author(s)
      Reina Nakajima, Masanori Tsuruta, Masayoshi Higuchi, Kimihisa Yamamoto
    • Journal Title

      J.Am.Chem.Soc.(ACS) 126

      Pages: 1630-1631

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Novel Poly(p-phenylene vinylene)s with a Phenylazo-methine Dendron as a Metal-Collecting Site2004

    • Author(s)
      Atsushi Kimoto, Kiriko Masachika, Jun-Sang Cho, Masayoshi Higuchi, Kimihisa Yamamoto
    • Journal Title

      Org.Lett.(ACS) 6

      Pages: 1179-1182

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of Asymmetrically Arranged Dendrimers with a Carbazole Dendron and a Phenylazomethine Dendron2004

    • Author(s)
      Atsushi Kimoto, Jun-Sang Cho, Masayoshi Higuchi, Kimihisa Yamamoto
    • Journal Title

      Macromolecules(ACS) 37

      Pages: 5531-5537

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Novel Triarylamine Dendrimers as a Hole transport Material with Controlled Metal-Assembling Function2003

    • Author(s)
      Yamamoto et al.
    • Journal Title

      J.Am.Chem.Soc. 125

      Pages: 8104-8105

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of Novel Phenylazomethine Dendrimers Having Cyclam Core and Their Zinc Complex2003

    • Author(s)
      Yamamoto et al.
    • Journal Title

      Organic Letters. 5

      Pages: 2547-2549

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of Novel Carbazole Dendrimers Having a Metal Coordination Site2003

    • Author(s)
      Yamamoto et al.
    • Journal Title

      Chemiatry Letters. 32

      Pages: 674-675

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Novel Triarylamine Dendrimers as a Hole transport Material with Controlled Metal-Assembling Function2003

    • Author(s)
      Norifusa Satoh, Jun-sang Cho, Masayoshi Higuchi, Kimihisa Yamamoto
    • Journal Title

      J.Am.Chem.Soc.(ACS) 125

      Pages: 8104-8105

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of Novel Phenylazo-methine Dendrimers Having Cyclam Core and Their Zinc Complex2003

    • Author(s)
      Osamu Enoki, Takane Imaoka, Kimihisa Yamamoto
    • Journal Title

      Org Lett.(ACS) 5

      Pages: 2547-2549

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of Novel Carbazole Dendrimers Having a Metal Coordination Site2003

    • Author(s)
      Atsushi Kimoto, Jun-Sang Cho, Masayoshi Higuchi, Kimihisa Yamamoto
    • Journal Title

      Chem.Lett. 32

      Pages: 674-675

    • Description
      「研究成果報告書概要(欧文)」より

URL: 

Published: 2006-07-11  

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