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A Study on the Synthesis, Structure, Reaction, and Properties of New π-Elecitronic Macrocycles

Research Project

Project/Area Number 14340200
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKyushu University

Principal Investigator

SHINMYOZU Teruo  Kyushu University, Institute for Materials Chemistry and Engineering, Professor, 先導物質化学研究所, 教授 (90037292)

Co-Investigator(Kenkyū-buntansha) SHIBAHARA Masahiko  Oita University, Faculty of Education and Welfare Science, Research Associate, 教育福祉学部, 助手 (60253762)
TAKEMURA Hiroyuki  Kyushu University, Faculty of Scieces, Research Associate, 理学部, 助手 (60183456)
Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥14,700,000 (Direct Cost: ¥14,700,000)
Fiscal Year 2003: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2002: ¥11,700,000 (Direct Cost: ¥11,700,000)
Keywordsprismanes / cage compounds / metallocene / cyclophane / charge transfer complexes / charge transfer interaction / conducting materials / photochemical reaction / プリズマン類 / 芳香族化合物 / ヘキサプリズマン / チューブ状分子 / フェロセン
Research Abstract

(1)Synthesis of hexaprismane derivatives via photo-isomerization of multibridged[3_n]cyclophanes(n=3-6)
Our efforts have been made toward the isolation and characterization of hexaprismane derivatives. In order to stabilize the hexaprismane skeleton and deactivate toward chemical reactions, we developed new synthetic methods of fluorinated[3_n]cyclophanes as precursor of the photochemical reactions. We confirmed that the photochemical reactions of these cyclophanes did proceed. The isolation and characterization of the photoproducts are in progress.
As an alternative method for the isolation of hexaprismane derivatives, we found that the[3_3]cyclophane is included in γ-cyelodextrine in 1:1 ratio and the complex is isolated. Irradiation of the complex in the solid state led to the formation of some cage compound(s), and their isolation and characterization are in progress.
2)Synthesis of tube-like molecules as new inclusion host molecules
For the construction of uni-molecular tube-like molecule, we synthesized the new cyclophanes with different cavity sizes as structural units and examined their structural properties. We are now studying connecting methods of these structural units. In connection with this study, we also designed and synthesized several three-dimensional new macrocycles via metal coordination.
(3)Synthesis and properties of metallocenes with cyclophane ligands
We have studied the synthetic route of [3_5]ferrocenophane in which an iron atom is highly compressed. As a new synthetic route, we designed to synthesize the ferrocenophane by the cyclization using olefin-metathesis. According to this route, synthesis is in progress.
We also studied the synthesis of mixed valent Ru(II)Ru(0)-[3_n]cyclophane(n=3,4) complexes as new electron-conducting materials. We found that the Ru(I)Ru(I) complex was formed by the two-electron reduction of the Ru(II)Ru(II)-[3_3]cyclophane complex, and examined its structure and chemical properties.

Report

(3 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] Rika Nogita et al.: "Photochemical Study of [3_3](1,3,5)Cyclophane and Emission Spectral Properties of [3_n]Cyclophanes (n=2-6)."J.Am.Chem.Soc.. (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] Gang Wen et al.: "A Conformational Study of 2,11-Diaza[3.3]metacyclophanes"J.Am.Chem.Soc.. (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] M.Zhou et al.: "An Aldol Approach to the Synthesis of [3_4](1,2,3,4)Ferrocenophane and its Structural and Electrochemical Properties"J.Organomet.Chem.. (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] Mikio Yasutake et al.: "Structural and Electric Properties of the Charge Transfer Complexes of 5,7,9-Trimethyl-and 2,11,20-trithia[3_3](1,3,5)cyclophanes."Eur.J.Org.Chem.. 1343-1347 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hiroyuki Takemura et al.: "A Comparison of Coordination Ability of Hetero atoms : a Li^+ and Na^+ Selective Pyridinophane-based Cryptand"Tetrahedron Lett.. 44. 5087-5089 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Katsuya Sako et al.: "Synthesis and Properties of Photo-responsive Tetrathiafulvalene Derivatives"Synthetic Metals. 137. 899-900 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Teruo Shinmyozu et al.: "CRC Handbook of Organic Photochemistry and Photobiology, 2^<nd> Edition(W.Horspool, F.Lenci(Eds))"CRC Press. 1000 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Rika Nogita et al.: "Photochemical Study of[3_3](1,3,5)Cyclophane and Emission Spectral Properties of[3_n]Cyclophanes (n=2-6)."J.Am.Chem.Soc.. (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] Gang Wen et al.: "A Conformational Study of 2,11-Diaza[3.3]metacyclophanes"J.Am.Chem.Soc.. (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] M.Zhou et al.: "An Aldol Approach to the Synthesis of[3_4](1,2,3,4)Ferrocenophane and its Structural and Electrochemical Properties"J.Organomet.Chem.. (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] Mikio Yasutake et al.: "Structural and Electric Properties of the Charge Transfer Complexes of 5,7,9-Trimethyl-and 2,11,20-trithia[3_3] (1,3,5)cyclophanes."Ear.J.Org.Chem.. 1343-1347 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hiroyuki Takemura et al.: "A Comparison of Coordination Ability of Hetero atoms : a Li^+ and Na^+ Selective Pyridinophahe-based Cryptand"Tetrahedron Lett.. 44. 5087-5089 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Katsuya Sako et al.: "Synthesis and Properties of Photo-responsive Tetrathiafulvalene Derivatives"Synthetic Metals. 137. 899-900 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Teruo Shinmyozu et al.: "CRC Handbook of Organic Photochemistry and Photobiology, 2^<nd> Edition(W.Horspool, F.Lenci(Eds)"CRC Press. (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Rika Nogita et al.: "Photochemical Study of [3_3](1,3,5)Cyclophane and Emission Spectral Properties of [3_n]Cyclophanes (n=2-6)"J.Am.Chem.Soc.. (in press). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Gang Wen et al.: "A Conformational Study of 2,11-Diaza[3.3]metacyclophanes"J.Am.Chem.Soc.. (in press). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Zhou et al.: "An Aldol Approach to the Synthesis of [3_4](1,2,3,4)Ferrocenophane and its Structural and Electrochemical Properties"J. Organoment.Chem.. (in press). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Mikio Yasutake et al.: "Structural and Electric Properties of the Charge Transfer Complexes of 5,7,9-Trimethyl-and 2,11,20-trithia[3_3] (1,3,5)cyclophanes"Eur.J.Org.Chem.. 1343-1347 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Hiroyuki Takemura et al.: "A Comparison of Coordination Ability of Hetero atoms : a Li^+ and Na^+ Selective Pyridinophane-based Cryptand"Tetrahedron Lett.. 44. 5087-5089 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Katsuya Sako et al.: "Synthesis and Properties of Photo-responsive Tetrathiafulvalene Derivatives"Synthetic Metals. 137. 899-900 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Teruo Shinmyouzu et al.(分担): "CRC Handbook of Organic Photochemistry and Photobiology, 2^<nd> Edition(W.Horspool, F.Lenci編集者)"CRC Press(出版社). 1000 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Mikio Yasutake et al.: "An Improved Synthetic Route of[3_5](1,2,3,4,5)Cyclophane, and Structural and Electric Properties of Charge Transfer Complexes of Multibridged[3_n]Cyclophane(n=3-6)in the Solid State"J. Am. Chem. Soc.,. 124. 10136-10145 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Teizi Satou et al.: "Synthesis and Structural Study of 2,11-Diaza[3.3](3,5)pryridinophane"J. Chem. Soc., Perkin Trans. 2. 393-397 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 野北里花, 新名主輝男: "光化学反応によるヘキサプリズマン誘導体の合成研究"光化学. 33巻2号. 106-113 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Mikio Yasutake et al.: "Solid State Structural Properties of Multibridged[3_n]Cyclophanes and Their Charge Transfer Complexes"Cyclophane Chemistry for the 21^<st> Century. 265-300 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Hiroyuki Takemura et al.: "Structurally Isomeric Two Pyridino Macrocycles : Complexation and Streuctures"Tetrahedron,. 59. 427-431 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Mikio Yasutake et al.: "Structural and Electric Properties of the Charge Transfer Complexes of 5,7,9-Trimenthyl-and 2,11,20-trithia[3_3](1,3,5)cyclophanes"Eur. J. Org. Chem.. (in press). (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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