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Synthesis, Structure, and Properties of New Conjugated pi-Electronic Systems

Research Project

Project/Area Number 09440221
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 Univ.Institute for Fundamental Research of Organic Chemistry, Associate Professor, 有機化学基礎研究センター, 助教授 (90037292)

Co-Investigator(Kenkyū-buntansha) TAKEMURA Hiroyuki  Kyushu Univ.Faculty of Science, Research Associate, 理学部, 助手 (60183456)
Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥12,000,000 (Direct Cost: ¥12,000,000)
Fiscal Year 1998: ¥2,600,000 (Direct Cost: ¥2,600,000)
Fiscal Year 1997: ¥9,400,000 (Direct Cost: ¥9,400,000)
Keywordscyclophane / hexaprismane / photochemical reaction / electronic conductor / annulene / transannular pi-pi interaction / decarbonylation reaction / pi-arene complexes / ヘキサブリズマン / 非経験的分子軌道法
Research Abstract

We have been studied transannular pi-pi interaction, conformational behavior, and photochemical properties of [3]superphane 1 and its lower homologs, multibridged [3_n]cyclophanes (n=3-5). Despite much effort, hexaprismane 3 has eluded synthesis so far. We studied the formation of the hexa-prismane skeleton by irradiating multibridged [3_n]cyclophanes. irradiation of [3_3 (1,3,5)cyclophane 2 with a low pressure Hg lamp in a water-saturated CH_2Cl_2 solution gave a new cage compound with bishomopentaprismane skeleton. Similarly [3_3](1,2,4,5)cyclophane 4 afforded a nove1 cage diol, whose skeleton is similar to that of diamantane. In both cases, irradiation may first afford highly strained hexaprismane derivatives, but they are immediately protonated to give cations, which are rearranged to the less strained cations. The most stable cations are intercepted by an attack of water to give hydroxyl compounds.
The multibridged [3_n]cyclophanes formed crystalline charge transfer complexes with TCNQ.The relative dependence of the electric conductivity on the stacking mode of the donar and acceptor was studied. The conductivity of the 1 : TCNQ (1 : 1) complex was low and this was ascribed to the alternate stacking of the donar and acceptor. The mono-nuclear Ru^<2+> and 0s^<2+> complexes of multibridged [3_n]cyclophanes (n=2-4) were synthesized and their electrocchemical properties were studied. Then di- nuclear Ru(II) complexes of 4 were synthesized and characterized, and their mixed-valance ion Ru(II)- Ru(O) was formed by the electrochemical reduction. Measurement of the conductivity is in progress.
We also developed novel synthetic reactions of cyclophanes such as photodecarbonylation and CO_2 insertion reactions.

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] Kenzi Hori: "Ab Initio Molecular Orbital Study on Inversion Mechanism of Trimethylene Bridges of [3_3](1,3,5)-and [3_6](1,2,3,4,5,6)Cyclophanes" Teterahedron Lett.38. 8955-8958 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hajime Isaji: "A New Synthetic Method of[2.2]Cyclophanes from[3.3]Cyclophane-2,ll-diones by the Photochemical Extrusion of Carbon Monooxide" Tetrahedron Lett.39. 4303-4304 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Youichi Sakamoto: "Synthesis,Structure,and Transannular π-π Interactions of Multibridged [3_n]Cyclophanes" Recent Research Developments in Pure and Applied Chemistry. 2. 371-399 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Teizi Satou: "The First Osmium(II),Ruthenium(II),and Iron(II) Complexes of [3_n]Cyclophanes (n=2-4): Synthesis and Electrochemical Study" J.Organomet.Chem.印刷中. (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Youichi Sakamoto: "Formation of Novel Cage Compounds via Photoreaction of [3_3](1,3,5)Cyclophane" Tetrahedron Lett.40. 919-922 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hiroyuki Takemura: "Stable Cu^+,Ag^+ Complexes of Aza-bridged Macrocyclic Molecules: Structures and Chemical Properties" J.Chem.Soc.Perkin Trans 1.239-246 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Kenzi Hori, Sento Wakana, and Teruo Shinmyozu: "Ab Initio Molecular Orbital Study on Inversion Mechanism of Tri-methylene Bridges of [3_3] (1,3,5) -and [3_6] (1,2,3,4,5,6) Cyclophanes" Teterahedron Lett.38. 8955-8958 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hajime Isaji, Katsuya Sako, Hiroyuki Takemura, and Teruo Shinmyozu: "A New Synthetic Method of [2.2] Cyclophanes from [3.3] Cyclo-phane-2,11-diones by the Photochemical Extrusion of Carbon Monooxide" Tetrahedron Lett.39. 4303-4304 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Youichi Sakamoto, and T.Shinmyozu: "Synthesis, Structure, and Transannular pi-pi Interactions of Multibridged [3_n] Cyclophanes" Recent Research Developments in Pure and Applied Chemistry. 2. 371-399 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Teizi Satou, Ko Takehara, Mihoko Hirakida, Youichi sakamoto, and Teruo Shinmyozu: "The First Osmium (II), Ruthenium (II), and Iron (II) Complexes of [3_n] Cyclophanes (n=2-4) : Synthesis and Electrochemical Study" J.Organomet.Chem.(in press). (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Youichi Sakamoto, Tsutomu Kumagai, Kumi Matohara, Chultack Lim, and Teruo Shinmyozu: "Formation of Novel Cage Compounds via Photoreaction of [3_3] (1,3,5) Cyclophane" Tetrahedron Lett.40. 919-922 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hiroyuki Takamura, Noriyoshi Kon, Ko Takehara, Junko Kimoto, Teruo Shinmyozu, and Takahiko Inazu: "Stable Cu^+, Ag^+ Complexes of Aza-bridged MacrocyclicMolecules : Structures and Chemical Properties" J.Chem.Soc.Perkin Trans. 1. 239-246 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Youichi Sakamoto: "Synthesis,Structure,and Transannular π-π Interactions of Multibridged (3_n) Cyclophanes" Recent Research Developments in Pure and Applied Chemistry. 2. 371-399 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Hajime Isaji: "A New Synthetic Method of(2,2)Cyclophanes from(3,3)Cyclophane-2,11- diones by the Photochemical Extrusion of Carbon Monooxide" Terahedron Lett.39. 4303-4303 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Youichi Sakamoto: "Formation of Novel Cage Compounds vis Photoreaction of(3.3.3)(1,3,5)-Cyclophane" Terahedron Lett.40. 919-922 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Teizi Satou: "The First Osmium(II),Ruthenium(II),and Iron(II)Complexes of(3_n)Cyclophanes (n=2-4):Synthesis and Electrochemical Study" J.Organomet.Chem.(印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Wakana Sentou: "Modified Synthetic Method,Structure,and Cycloaddition Reactivity of (3_4)(1,2,4,5)Cyclophane." Eur.J.Org.Chme.(印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Hiroyuki Takemura: "Potassium Complexes of Fluorine Containing Macrocyclic Cage Comound: Interactions Between Fluorine and Metal ions" Angew.Chem.Int.Ed.Engl.(印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Hiroyuki Takemura: "Stable Cu^+,Ag^+ Complxes of Aza-bridged Macrocyclic Molecules:Structures and Chemical Properties" J.Chem.Soc.Perkin Trans 1. 239-246 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Teruo Shinmyozu: "Ab Initio Molecular Orbital Study on Inversion Mechanism of Trimethylene Bridges of [3_3](1,3,5)-and[3_6](1,2,3,4,5,6)Cyclophanes" Tetrahedron Lett.38. 8955-8958 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Teruo Shinmyozu: "Synthesis,Structure,and Transannular π-π Interactions of Multibridged [3n]Cyclophanes" Recent Research Developments in Pure and Applied Chemistry. (印刷中). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Teruo Shinmyozu: "The First Osmium(II),ruthenium(II),and Iron(II)Complexes of[3_n]Cyclophanes(n=2-4)Synthesis and Electrochemical Study" J.Organomet.Chem.(印刷中). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Teruo Shinmyozu: "A New Synthetic Method of [2,2]Cyclophanes from [3,3]Cyclophane-2,11-diones by the Photochemical Extrusion of Carbon Monooxide" Tetrahedron Lett.(印刷中). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Teruo Shinmyozu: "Synthesis of Novel Cage Compounds via Photoreaction of[3_3](1,3,5)Cyclophane" Tetrahedro Lett.(印刷中). (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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