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Research on Synthesis and Properties of Hybridized System between Dihexylbithiophene and Octaethylporphyrin (OEP-DHBT-OEP) Connected with the 1,3-Diacetylene Linkages

Research Project

Project/Area Number 11640528
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

HIGUCHI Hiroyuki  DEPARTMENT OF CHEMISTRY, FACULTY OF SCIENCE, TOYAMA UNIVERSITY, ASSOCIATE PROFESSOR, 理学部, 助教授 (00165094)

Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2000: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1999: ¥1,800,000 (Direct Cost: ¥1,800,000)
KeywordsEglinton condition / oxidative cross-coupling / porphyrin / thiophene / orientation / anisotropy / electron-releasing ability / self-association / ビチオフェン / クロスカップリング / 拡張共役系 / 融合体 / 電子構造
Research Abstract

The extended hybridized OEP-DHBT-OEP system has been successfully synthesized by oxidative cross-coupling reactions of the corresponding terminal acetylenes under the modified Eglinton conditions. Under the same reaction conditions as for the symmetrical isomers, the more extended system describable as OEP-(DHBT)_n-OEP (n=2-5) could be simultaneously obtained as characterizable products in moderate yields, in consequence of the higher reactivity of the bis (ethynyl) DHBT than the meso-ethynyl OEP.From the ^1H NMR spectral studies of their molecular structures, it was suggested that the anisotropy by Ni-OEP ring current effect influences the Th-H located in a deshielded region within the limits of ca. 25 Å. Electronic absorption spectral properties of the OEP-DHBT-OEP system were examined, clearly proving that the orientation of DHBT plays an important role in electronic communications between the two terminal OEP rings. The HH isomer exhibited a broad Soret band, seemingly characterist … More ic of a dimeric property of the 3HTh-OEP system, while the TT isomer split Soret band into two clear bands characteristic of an intensive electronic interaction between the two terminal Ni-OEP rings. In the case of the OEP-(DHBT)_n-OEP system, it was indicated that the HH series gradually separate their electronic structures into two main components ; the diacetylene-group connected 3HTh-OEP component and the remaining (HH DHBT)_n component. On the other hand. the TT series were tentatively proposed to converge into an electronic structure hybridized between the diacetylene-group connected OEP-(TT DHBT) component and the remaining (TT DHBT)_n component, while retaining their molecular planarities. The electrochemical studies of the OEP-(DHBT)_n-OEP system showed that the compounds with n=1 exhibited the higher electron-releasing abilities with increasing the conjugation planarities of DHBT, in order of HH<HT<TT.It was proved that the electron-releasing abilities and electron-transfer processes for the compounds with more than n=2 are also determined by the extension magnitudes of the π-electronic conjugation system, reflecting both of the orientations and numbers of DHBT.It is also suggested that the OEP-DHBT-OEP system associates with each other in a highly concentrated solution, reflecting an orientation of DHBT.Continuous investigations of the self-association, however, are necessary for an elucidation of the electronic interactions betwecn the two terminal Ni-OEP rings both intra-and intermolecularly, in connection with the self-association effect on their electronic and electrochemical properties. Less

Report

(3 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] Higuchi,H.: "Synthesis and Properties of Head-to-head, Head-to-tail, and Tail-to-tail Orientational Isomers of Extended Dihexylbithiophene-Octaethylporphyrin System [OEP-(DHBT)_n-OEP]Connected with 1,3-Butadiyne Linkages"Bull.Chem.Soc.Jpn.. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Higuchi,H.: "Synthesis and Structural and Electronic Properties of the Mixed Complexes of Vinylene-bridged Bis-and Tris(octaethylporphyrin)s with Ni(II), Pd(II), and Pt(II)Ions"Bull.Chem.Soc.Jpn.. 73. 1259-1275 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hernandez,V.: "Combined Theoretical and Vibrational Study of Dihexylbithienoquinonoid Derivatives with Regioregular Head-to-head, Head-to-tail and Tail-to-tail Orientations"J.Physical Chem.. 104. 661-672 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Higuchi,H.: "Synthesis and Properties of Orientational Isomers of Hybridized Dihexylbithiophene-Octaethylporphyrin Connected with 1,3-Butadiyne Linkages"Tetrahedron Lett.. 40. 9091-9095 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Higuchi, H., Ishikura, T., Mori, K., Takayama, Y., Yamamoto, K., Tani, K., Miyabayashi, K., Miyake, M.: "Synthesis and Properties of Head-to-head, Head-to-tail, and Tail-to-tail Orientational Isomers of Extended Dihexylbithiophene-Octaethylporphyrin System [OEP-(DHBT)_n-OEP] Connected with 1,3-Butadiyne Linkages"Bull.Chem.Soc.Jpn.. in press.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Higuchi.H., Shinbo, M., Usuki, M., Takeuchi, M., Tani, K., Yamamoto, K.: "Synthesis and Structural and Electronic Properties of the Mixed Complexes of Vinylene-bridged Bis- and Tris (octaehylporphyrin)s with Ni(II), Pd(II), and Pt(II) Ions"Bull.Chem.Soc.Jpn.. 73. 1259-1275 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hernandez, V., Lasada, S.C., Casado, J., Higuchi, H., Navarrete, J.T.L.: "Combined Theoretical and Vibrational Study of Dihexylbithienoquinonoid Derivatives with Regioregular Head-to-head, Head-to-tail and Tail-to-tail Orientations"J.Physical Chem.. 104. 661-672 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Higuchi, H., Ishikura.T., Miyabayashi, K., Miyake, M., Yamamoto, K.: "Synthesis and Properties of Orientational Isomers of Hybridized Dihexylbithiophene-Octaethylporphyrin Connected with 1,3-Butadiyne Linkages"Tetrahedron Lett.. 40. 9091-9095 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Higuchi,H.: "Synthesis and Properties of Head-to-head, Head-to-tail, and Tail-to-tail Orientational Isomers of Extended Dihexylbithiophene-Octaethylporphyrin System [OEP-(DHBT)_<11>-OEP] Connected with 1.3-Butadiyne Linkages"Bull.Chem.Soc.Jpn.. (印刷中).

    • Related Report
      2000 Annual Research Report
  • [Publications] Higuchi,H.: "Synthesis and Structural and Electronic Properties of the Mixed Complexes of Vinylene-bridged Bis- and Tris(octaethylporphyrin)s with Ni(II), Pd(II), and Pt(II)Ions "Bull.Chem.Soc.Jpn.. 73・5. 1259-1275 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Hernandez, V.: "Combined Theoretical and Vibrational Study of Dihexylbithienoquinonoid Derivatives with Regioregular Head-to-head, Head-to-tail and Tail-to-tail Orientations"J.Physical Chem.. 104・3. 661-672 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Higuchi,H.: "Synthesis and Properties of Orientational Isomers of Hybridized Dihexylbithiophene-Octaethylporphyrin Connected with 1,3-Butadiyne Linkages"Tetrahedron Lett.. 40・51. 9091-9095 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Higuchi H.他4名: "Synthesis and Properties of Orientational Isomers of Hybridized Dihexylbithiophene-Octaethylporphyrin Connected with 1,3-Butadiyne Linkages"Tetrahedron Letters. 40. 9091-9095 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Higuchi H.他5名: "Synthesis and Electronic Properties of d^8 Transition-Metal Complexes of Vinylene-Bridged Bis- and Tris(octaethylporphyrin)s"Bull. Chem. Soc. Jpn.. 72. 1887-1898 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Higuchi H.他4名: "Synthesis and Electronic Absorption Spectra of Orientational Isomers of Bithiophene Derivatives Bridged with 1,3-Butadiyne Linkages"Nonlinear Optics. 22. 337-340 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Higuchi H.他3名: "Synthesis and Electronic Properties of Ni-Pd-Pt Complex of Vinylene-bridged Tris(octaethylporphyrin)"Nonlinear Optics. 22. 333-336 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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