2000 Fiscal Year Final Research Report Summary
Research on Synthesis and Properties of Hybridized System between Dihexylbithiophene and Octaethylporphyrin (OEP-DHBT-OEP) Connected with the 1,3-Diacetylene Linkages
| Project/Area Number |
11640528
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Toyama University |
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Principal Investigator |
HIGUCHI Hiroyuki DEPARTMENT OF CHEMISTRY, FACULTY OF SCIENCE, TOYAMA UNIVERSITY, ASSOCIATE PROFESSOR, 理学部, 助教授 (00165094)
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| Project Period (FY) |
1999 – 2000
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| Keywords | Eglinton condition / oxidative cross-coupling / porphyrin / thiophene / orientation / anisotropy / electron-releasing ability / self-association |
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| 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
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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
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[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.
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「研究成果報告書概要(欧文)」より
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[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)
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「研究成果報告書概要(欧文)」より
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[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
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