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2007 Fiscal Year Final Research Report Summary

Syntheses of Innovative Porous Metal Complexes and Their Functional Chemistry

Research Project

Project/Area Number 16074209
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionKyoto University

Principal Investigator

KITAGAWA Susumu  Kyoto University, Institute for Integrated Cell-Material Sciences, Deputy Director (20140303)

Co-Investigator(Kenkyū-buntansha) OHBA Masaaki  Kyoto University, Graduate school of Engineering, Associate Professor (00284480)
CHANG Ho-Chol  Kyoto University, Graduate school of Engineering, Assistant Professor (60335198)
UEMURA Takashi  Kyoto University, Graduate School of Engineering, Assistant Professor (50346079)
INAGAKI Shinji  Kyoto University, Toyota Central R&D Labs., Inc., Group Leader (30374086)
Project Period (FY) 2004 – 2007
KeywordsPorous metal complexes / multi-functions / polymer synthesis / mesoporous silica
Research Abstract

In this project, we aim to develop functions with the characteristics of porous coordination polymers (PCPs)such as designable surface functionality, high regularity, and framework flexibility Highly controlled acetylene accommodation in a microporous coordination polymer has been accomplished by preparing a pore surface specific for acetylenic hydrogen atoms. The acetylene can be packed 200 times as densely as the limitation value without explosion. The adsorbed acetylene molecules are highly stabilized by the double hydrogen bonded supports in nanosized pores, which mere revealed by direct observation of the adsorbed molecules using the results of in-situ synchrotron XRD measurements and by first principles calculations.
We have designed and synthesized a bimodal microporous twofold interpenetrating PCP with two types of channel for anionic N(CN)2- and neutral water molecules, respectively. The dehydrated framework provides a dual function of specific anion exchange of free N(CN)2- for the smaller N3- anions and selective gas sorption. The N3--exchanged framework leads to a dislocation of the mutual positions of the two interpenetrating frameworks, resulting in an increase in the effective pore size in one of the counterparts of the channels and a higher accommodation of adsorbate than in the as-synthesized framework.
A few substituted acetylenes spontaneously polymerized in one-dimensional nanochannels of PCPs with pillared layer structure. In this polymerization system, only mono-substituted acetylenes with electron-withdrawing group could be polymerized in the channels. suggesting that strong hydrogen bonding interaction between the monomers and surface carboxylate moiety in the frameworks is a key factor to initiate the polymerization.

  • Research Products

    (9 results)

All 2007 2006 2005

All Journal Article (7 results) (of which Peer Reviewed: 4 results) Presentation (2 results)

  • [Journal Article] Guest-Specific Function of a Flexible Undulating Channel in a 7, 7, 8, 8-Tetracyano-p-quinodimethane Dimer-Based Porous Coordination Polymer2007

    • Author(s)
      S. Shimomura, S. Horike, R. Matsuda, S. Kitagawa
    • Journal Title

      J. Am. Chem. Soc. 129

      Pages: 10990-10991

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Topotactic Linear Radical Polymerization of Divinylbenzenes in Porous Coordination Polymers2007

    • Author(s)
      T. Uemura, D. Hiramatsu, Y. Kubota, M. Takata, S. Kitagawa
    • Journal Title

      Angew. Chem. Int. Ed. 46

      Pages: 4987-4990

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Topotactic Linear Radical Polymerization of Divinylbenzenes in Porous Coordination Polymers2007

    • Author(s)
      T. Uemura, D. Hiramatsu, Y. Kubota, M. Takata, S. Kltagawa
    • Journal Title

      Angew. Chem. Int. Ed. 46

      Pages: 4987-4990

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Guest Induced Asymmetry in a Metal-Organic Solid with Reversible Single-Crystal-to-Single-Crystal Structural Transformation2006

    • Author(s)
      T. K. Maji, G. Mostafa, R. Matsuda, S. Kitagawa
    • Journal Title

      J. Am. Chem. Soc. 127

      Pages: 17152-17153

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Guest Induced Asymmetry in a Metal-Organic Solid with Reversible Single-Crystal-to-Single-Crystal Structural Transfomation2006

    • Author(s)
      T. K. Maji, G. Hostafa, R. Matsuda, S. Kitagawa
    • Journal Title

      J. Am. Chem. Soc. 127

      Pages: 17152-17153

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Highly controlled acetylene accommodation in a metal-organic microporous material2005

    • Author(s)
      24) R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota, R. V. Belosludov, T. C. Kobayashi, H. Sakamoto, T. Chiba, M. Takata, Y. Kawazoe, Y. Mita
    • Journal Title

      Nature 436

      Pages: 238-241

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Highly controlled acetylene accommodation in a metal-organic microporous material2005

    • Author(s)
      R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota, R. V. Belosludov, T. C. Kobayashi, H. Sakamoto, T. Chiba, M. Takata, Y. Kawazoe, Y. Mita
    • Journal Title

      Nature 436

      Pages: 238-241

    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Flexible Coordination Polymers as Novel Porous Materials2005

    • Author(s)
      S. Kitagawa
    • Organizer
      The 17th edition of the International Conference on the Chemistry of the Organic Solid State (ICCOSS, XVII) (Plenary Talk).
    • Place of Presentation
      Los Angels, U.S.A.
    • Year and Date
      20050700
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Flexible Coordination Polymers as Novel Porous Materials2005

    • Author(s)
      S. Kitagawa
    • Organizer
      The 17th edition of the International Conference on the Chemistry of the Organic Solid State (ICCOSS, XVII)
    • Place of Presentation
      Los Angels, U.S.A.
    • Year and Date
      2005-07-27
    • Description
      「研究成果報告書概要(和文)」より

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Published: 2010-06-09  

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