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Creation of New Molecular Assemblies by Noncovalent Bonding Abilities of Thioamides

Research Project

Project/Area Number 15550103
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Polymer chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

KANBARA Takaki  Tokyo Institute of Technology, Chemical Resources Laboratory, Associate Professor, 資源化学研究所, 助教授 (90204809)

Project Period (FY) 2003 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2005: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2004: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2003: ¥1,600,000 (Direct Cost: ¥1,600,000)
KeywordsThioamide / Hydrogen bond / Coordination / Macrocyclic compound / Metal complexes / Molecular assembly / Receptor / Pseudorotaxane / 環状化合物 / 高分子 / 重金属捕集
Research Abstract

Thionation of macrocyclic polylactams gave new macrocyclic polythiolactams. The chemical transformation enhanced hydrogen-bonding ability of the N-H protons in the cavity, and provided a strong affinity toward hydrogen-acceptors such as anions, amides, and esters. The association properties of the macrocyclic receptors were examined by ^1H NMR titration. The molecular structures of the inclusion complexes and [2]pseudorotaxanes were determined by X-ray crystallography. Threading and dethreading process of the [2]pseudorotaxanes was also been examined.
Ortho, ortho-Cyclometalation of 1,3-benzenedicarbothioamides afforded κ^3S, C, S and κ^3S, N, S pincer complexes. The complexes formed supramolecular networks through intermolecular N-H【triple bond】Cl hydrogen bonds. X-ray crystallography revealed that the solvent molecules included in the crystal assisted formation of the supramolecular networks. The complexes exhibit strong emission on a glassy frozen state as well as in the solid state. The decay lifetime of the emission from the complexes is indicative of phosphorescent emission.
Willgerodt-Kindler type reactions of dialdehydes and diamines in the presence of sulfur readily provided polythioamides. The polymers could effectively collect precious metals such as Au(III), Pt(IV), and Pd(II) from not only aqueous but also organic solutions. Selective adsorption and separation of group 10 metal ions (Ni(II), Pd(II), and Pt(IV)) from the mixture solutions were achieved by the polymers. The molecular structure of model complex revealed that intermolecular C=S【triple bond】M coordination afforded the selective adsorption properties. The collection of Au(III) from synthetic organic liquid waste was also demonstrated.

Report

(4 results)
  • 2005 Annual Research Report   Final Research Report Summary
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (23 results)

All 2006 2005 2004 2003 Other

All Journal Article (16 results) Book (1 results) Patent(Industrial Property Rights) (3 results) Publications (3 results)

  • [Journal Article] Synthesis and Structural Features of a Series of κ^3SNS Pincer Complexes of Group 10 Metals σ-Bonded to Centered Pyrrolate Unit2006

    • Author(s)
      Ken Okamoto
    • Journal Title

      Chem. Lett. 35

      Pages: 558-559

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Synthesis and Structural Features of a Series of κ^3SNS Pincer Complexes of Group 10 Metals σ-Bonded t Centered Pyrrolate Unit2006

    • Author(s)
      Ken Okamoto et al.
    • Journal Title

      Chem.Lett. 35

      Pages: 558-559

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Luminescent Palladium Complexes Containing Thioamide-Based SCS Pincer Ligands2005

    • Author(s)
      Michinori Akaiwa
    • Journal Title

      J. Organomet. Chem. 690

      Pages: 4192-4196

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Luminescent Palladium Complexes Containing Thioamide-Based SCS Pincer Ligands2005

    • Author(s)
      Michinori Akaiwa et al.
    • Journal Title

      J.Organomet.Chem. 690

      Pages: 4192-4196

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Luminescent Palladium Complexes Containing Thioamide-Based SCS Pincer Ligands2005

    • Author(s)
      Michinori Akaiwa
    • Journal Title

      J.Organomet.Chem. 690

      Pages: 4192-4196

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Azacalix[n]arenes with -NH- Amino Group : NH・・・OCH_3 Interaction-Assisted Synthesis, Structure, and Reactivity2005

    • Author(s)
      Wataru Fukushima
    • Journal Title

      Synlett No.19

      Pages: 2931-2934

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Construction of New [2]Pseudorotaxanes by Hydrogen Bonding Assembly of Macrocyclic Tetrathiolactam with Amides and an Ester2004

    • Author(s)
      Yoshihiko Inoue
    • Journal Title

      Tetrahedron Letters 45

      Pages: 4603-4606

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary 2004 Annual Research Report
  • [Journal Article] Preparation of Platinum Complexes Containing a Thioamide-Based SCS Pincer Ligand and Their Light Emitting Properties2004

    • Author(s)
      Takaki Kanbara
    • Journal Title

      J. Organomet. Chem. 689

      Pages: 1860-1864

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Construction of New [2]Pseudorotaxanes by Hydrogen Bonding Assembly of Macrocyclic Tetrathiolactam with Amides and an Ester2004

    • Author(s)
      Yoshihiko Inoue et al.
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 4603-4606

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Preparation of Platinum Complexes Containing a Thioamide-Based SCS Pincer Ligand and Their Light Emitting Properties2004

    • Author(s)
      Takaki Kanbara et al.
    • Journal Title

      J.Organomet.Chem. 689

      Pages: 1860-1864

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Preparation of Platinum Complexes Containing a Thioamide-Based SCS Pincer Ligand and Their Light Emitting Properties2004

    • Author(s)
      Takaki Kanbara
    • Journal Title

      J.Organomet.Chem. 689

      Pages: 1860-1864

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Preparation of a New Receptor for Anions, Macrocyclic Polythiolactam - Structure and High Anion Binding Ability2003

    • Author(s)
      Yoshihiko Inoue
    • Journal Title

      Tetrahedron Lett. 44

      Pages: 5167-5169

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Polythioamide as a Collector for Valuable Metals from Aqueous and Organic Solutions2003

    • Author(s)
      Shigehiro Kagaya
    • Journal Title

      Chem. Lett. 32

      Pages: 622-623

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Preparation of a New Receptor for Anions, Macrocyclic Polythiolactam - Structure and High Anion Binding Ability2003

    • Author(s)
      Yoshiko Inoue et al.
    • Journal Title

      Tetrahedron Lett. 44

      Pages: 5167-5169

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Polythioamide as a Collector for Valuable Metals from Aqueous and Organic Solutions2003

    • Author(s)
      Shigehiro Kagaya et al.
    • Journal Title

      Chem.Lett. 32

      Pages: 622-623

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Preparation and Characterization of Luminescent SCS and NCN Pincer Platinum Complexes Derived from 3,5-Bis(anilinothiocarbonyl)toluene

    • Author(s)
      Ken Okamoto et al.
    • Journal Title

      Organometallics (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Book] Focus on Organometallic Chemistry Research (分担)2006

    • Author(s)
      Takaki Kanbara
    • Publisher
      Nova Science Publishers Inc.
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 金属の分離回収方法2005

    • Inventor(s)
      神原貴樹, 加賀谷重浩
    • Industrial Property Rights Holder
      東京工業大学, 富山大学
    • Filing Date
      2005-05-25
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 金属の分離回収方法2005

    • Inventor(s)
      神原 貴樹
    • Industrial Property Rights Holder
      東京工業大学, 富山大学
    • Industrial Property Number
      2005-152663
    • Filing Date
      2005-05-25
    • Related Report
      2005 Annual Research Report
  • [Patent(Industrial Property Rights)] アザカリックスアレーンおよびその製造法2005

    • Inventor(s)
      神原 貴樹
    • Industrial Property Rights Holder
      東京工業大学
    • Industrial Property Number
      2005-243885
    • Filing Date
      2005-08-25
    • Related Report
      2005 Annual Research Report
  • [Publications] Yoshihiko Inoue: "Preparation of a New Receptor for Anions, Macrocyclic Polythiolactam - Structure and High Anion Binding Ability"Tetrahedron Lett.. 44. 5167-5169 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Shigehiro Kagaya: "Polythioamide as a Collector for Valuable Metals from Aqueous and Organic Solutions"Chem.Lett.. 32. 622-623 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Takaki Kanbara: "Synthesis, Molecular Structure, and Photoluminescence Properties of Palladium and Platinum Complexes Containing Phosphine Sulfide-Based SCS Pincer Ligand"J.Organomet.Chem.. 688. 15-19 (2003)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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