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Fixation of functional Molecules Confined to One-dimentional Porous Crystal with Nanometer-scale Quantum Channels

Research Project

Project/Area Number 13440201
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionOsaka City University

Principal Investigator

TADOKORO Makoto  Osaka City University, Graduate School of Science, Professor, 大学院・理学研究科, 助教授 (60249951)

Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥11,000,000 (Direct Cost: ¥11,000,000)
Fiscal Year 2003: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2002: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2001: ¥8,200,000 (Direct Cost: ¥8,200,000)
KeywordsHydrogen Bond / Ziolite / Crystal Engineering / Supra-molecular Chemistry / Nanosience / Ruthenium Complex / Molecular Crystal / Electrochemistry / 水 / 超分子 / ポーラスクリスタル / プロトン伝導 / 水分子クラスター / 氷多形 / 多孔質結晶 / 金属錯体 / 水クラスター / 氷-水相転移 / カルボン酸 / ポーラス結晶 / Crystal Engineering
Research Abstract

Research on microporous solids has focused largely on inorganic materials such as zeolites. Although syntheses of fragments of these prototypes have been achieved, extensions to three-dimensional networks by conventional synthesis have been difficult to realize. One approach to rational design of such networks with these fragments has been achieved by using the coordinating and intermolecular hydrogen-bonding properties, the geometly, and the composition of transition metal complexes which are naturally predisposed to form a certain array of several well categorized solid networks. A goal of this research has been the design of new functional materials without restraint at the properties of zeolite such as selective adsorption and catalytic activity. The tools of molecular synthesis of hydrogen-bonded coordination compounds would be useful to engineer new types of microporous solids constructed by transition metal ions and hydrogen bonding. A design based on a modular approach using bu … More ilding blocks [M^<III>(Hbim)_3] (M = Co) and trimesic acids forms a crystal structure with extended honeycomb sheets (diameter of porosity ca. 16Å). The whole structure with 1-D channels results from stacking of the layers along the c axis. In this study we have placed nanometer-scale water clusters within the porous crystal formed from molecular blocks specifically designed to investigate the molecular dynamics of confined water molecules. X-ray crystallography of a crystal filled with water has demonstrated that water clusters found in a one-dimensional nanochannel consist of multi-layered water structure with hydrogen bonding networks. The water-tubes exhibit continuous dynamics resembling a water-ice transition, which produces a "three-layered ice" state below Ca. -38℃. In the ice state, we have observed novel fragments of water clusters in a cubic ice phase I_c of similar structure. The fragment was recognized as a distinct structural model of the crystal embryo in heterogeneous nucleation on an ice I_c. Furthermore, they demonstrated the existence of a unique water tetramer containing water molecules with three nearest neighbouring hydrogen bonds without normal tetrahedral ones. Less

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report

Research Products

(21 results)

All Other

All Publications

  • [Publications] 田所 誠: "総説「水素結合型金属錯体を用いた結晶設計と配列制御」"有機合成化学会誌. 62(in press). (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Morita, T.Murata, K.Fukui, M.Tadokoro, K.Sato, D.Shiomi, T.Takui, K.Nakasuji: "The First Metal complexes of 4.4'-Biimidazole and 4,4'-Biimidazolate with Hydrogen-Bonding Networks on the Cu(II) Complexes : 1-D Structures by N-H…X…H-N Hydrogen-Bonding"Chem.Lett.. 33. 188-189 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 田所 誠: "Review「ビイミダゾール型分子間水素結合を利用した金属錯体のクリスタルエンジニアリング」"日本結晶学会誌. 45. 240-248 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Morita, T.Murata, S.Yamada, M.Tadokoro, A.Ichimura, K.Nakasuji: "Novel building blocks for crystal engineering : the first synthesis of oligo(imidazole)s"J.Chem.Soc., Perkin Trans.1. 2598-2600 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Tadokoro, H.Kanno, T.Kitajima, H.S-.Umemoto, N.Nakanishi, K.Isobe, K.Nakasuji: "Self-Organizing Super-Structures Fomed From Hydrogen-Bonded Biimidazolate Metal Complexes"Proc.Natl.Acad.Sci.USA. 99. 4950-4955 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Tadokoro, T.Shiomi, K.Isobe, K.Nakasuji: "Caesium (I) mediated 3-D super-structures by one-pot self-organization of hydrogen-bonded nickel complexe"Inorg.Chem.. 40. 5476-5478 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Makoto Tadokoro: "Molecular Designs for Self-Organized Superstructures, Dekker Encyclopedia of Nanoscience and Nanotechnology(Edited by J.A.Schwarz, C.Contescu, and K.Putyera)"2057-2066 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Tadokoro: "Crystal Engineering and Controlled Crystal Allays Using Hydrogen bonding Biimidozolate Metsl Complexe"J.Syn.Org.Chem.Jpn. 62(in press). (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Morita, T.Murata, K.Fukui, M.Tadokoro, K.Sato, D.Shiomi, T.Takui, K.Nakasuji: "The First Metal Complexes of 4,4'-Biimidazole and 4,4'-Biimidazolate with Hydrogen-Bonding Networks on the Cu(II) Complexes : 1-D Structures by NH…X…HH Hydrogen-Bonding"Chem.Lett.. 33. 188-189 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Tadokoro: "Crystal Engineering Using Complementary Intermolecular Hydrogen Bondings on Transition Metal Complexes with Biimidazolate Ligands"J.Crystallogr.Soc.Jpn. 45. 240-48 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Morita, T.Murata, S.Yamada, M.Tadokoro, A.Ichimura, K.Nakasuji: "Novel building blocks for crystal engineering : the first synthesis of oligo(imidazole)s"J.Chem.Soc., Perkin Trans. 1. 2598-2600 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Tadokoro H.Kanno, T.Kitajima, H.S-.Umemoto, N.Nakanishi, K.Isobe, K.Nakasuji: "Self-Organizing Super-Structures Fomed from Hydrogen-Bonded Biimidazolate Metal Complexes"Proc.Natl.Acad.Sci.USA. 99. 4950-4955 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Tadokoro, T.Shiomi, K.Isobe, K.Nakasuji: "Caesium (I) mediated 3-D super-structures by one-pot self-organization of hydrogen-bonded nickel complexes"Inorg.Chem.. 40. 5476-5478 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Tadokoro: "Molecular Designs for Self-Organized Superstructures Edited by J.A.Schwarz, C.Contescu, and K.Putyera"Dekker Encyclopedia of Nanoscience and Nanotechnology. 2057-2066 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 田所 誠: "Review「ビイミダゾール型分子間水素結合を利用した金属錯体のクリスタルエンジニアリング」"日本結晶学会誌. 45. 240-248 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Morita, T.Murata, S.Yamada, M.Tadokoro, K.Nakasuji: "Novel Oligoimidazoles for Hydrogen-bonded Charge-Transfer Complexes"Molecular Crystals and Liquid Crystals. 379. 83-88 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Tadokoro, H.Kanno, T.Kitajima, H.S.-Umemoto, N.Nakanishi, K.Isobe, K.Nakasuji: "Self-Organizing Super-Structures Fomed From Hydrogen-Bonded Biimidazolate Metal Complexes"Proc.Natl.Am.Soc.USA. 99. 4950-4955 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Yoshikawa, K.Kaawabe, M.Tadokoro, Y.suzuki, N.Yanagihara, A.Nakayama, H.Sakurai, Y.Kojima: "New Zinc (II) Complexes with Tetradentate Amono Acids Derivatives : Structure Characterization, Solution Chemistry, and in vitro Insulinomimetic Activity"Bull.Chem.Soc.Jpn. 75. 2423-2432 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Morita, T.Murata, S.Yamada, M.Tadokoro, A.Ichimura, K.Nakasuji: "Novel building blocks for crystal engineering : the first synthesis of oligo(imidazole)s"J.Chem.Soc., Perkin Trans.1. 2598-2600 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Tadokoro, T.Shiomi, et al.: "Caesium (I) mediated 3-D super-structures by one-pot self-organization of hydrogen-bonded nickel complexes"Inorganic Chemistry. 40. 5476-5478 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Tadokoro, H.Kanno, et al.: "Self-Organizing Super-Structures Fomed From Hydrogen-Bonded Biimidazolate Metal Complexes"The Proceedings of the National Academy of Sciences. (in press).

    • Related Report
      2001 Annual Research Report

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Published: 2001-03-31   Modified: 2016-04-21  

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