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

1,3-二乙炔键联二己基联噻吩与八乙基卟啉杂化体系(OEP-DHBT-OEP)的合成及性能研究

• 批准号: 11640528
• 负责人: HIGUCHI Hiroyuki
• 金额: $ 2.18万
• 依托单位: Toyama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640528/
• 关键词: Eglinton 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

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

在改进的埃格林顿条件下，通过末端乙炔的氧化偶联反应，成功地合成了OEP-DHBT-OEP杂化体系。在与对称异构体相同的反应条件下，由于双（乙炔基）DHBT的反应活性高于meso-乙炔基OEP，可同时以中等产率得到可描述为OEP-（DHBT）_n-OEP（n=2-5）的更扩展体系。结果表明，Ni-OEP环电流效应引起的各向异性在约100 nm范围内影响位于去屏蔽区的Th-H。25英里。研究了OEP-DHBT-OEP体系的电子吸收光谱性质，证明了DHBT的取向对OEP环两端的电子通讯起着重要的作用. HH异构体显示宽Soret带，似乎是其特征。 ...更多信息 IC的二聚体性质的3 HTh-OEP系统，而TT异构体分裂Soret带成两个明确的频带之间的两个终端Ni-OEP环的强烈的电子相互作用的特征。在OEP-（DHBT）_n-OEP体系中，HH系列的电子结构逐渐分离为两个主要组分：二乙炔基连接的~ 3 HTh-OEP组分和剩余的（HH DHBT）_n组分。从另一方面来说。TT系列聚合成一种电子结构，这种电子结构是由二乙炔基连接的OEP-（TTDHBT）组分和剩余的（TTDHBT）_n组分杂化而成，同时保持了分子的平面性。OEP-（DHBT）_n-OEP体系的电化学研究表明，随着DHBT共轭平面的增大，n=1的化合物释放电子的能力增大，其大小顺序为HH<HT<TT.对于n=2以上的化合物，其释放电子的能力和电子转移过程也取决于π电子共轭体系的扩展程度. OEP-DHBT-OEP体系在高浓度溶液中相互缔合，反映了DHBT的取向。然而，对自缔合的研究对于阐明两个末端Ni-OEP环之间的分子内和分子间的电子相互作用是必要的，与它们的电子和电化学性质的自缔合效应有关。少

项目成果

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)

Higuchi H. 和其他 4 人：“与 1,3-丁二炔键连接的杂化二己基联噻吩-八乙基卟啉的定向异构体的合成和性质”四面体快报 40. 9091-9095 (1999)。

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)

Higuchi, H.、Ishikura.T.、Miyabayashi, K.、Miyake, M.、Yamamoto, K.：“与 1,3-丁二炔键连接的杂化二己基联噻吩-八乙基卟啉的定向异构体的合成和性质”Tetrahedron Lett..

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)

Higuchi H. 和其他 3 人：“亚乙烯基桥联三（八乙基卟啉）的 Ni-Pd-Pt 配合物的合成和电子性能”非线性光学 22. 333-336 (1999)

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 Syste

Higuchi, H.、Ishikura, T.、Mori, K.、Takayama, Y.、Yamamoto, K.、Tani, K.、Miyabayashi, K.、Miyake, M.：“头对头的合成和性质

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)

Higuchi, H.：“亚乙烯基桥联的双和三（八乙基卟啉）与 Ni(II)、Pd(II) 和 Pt(II) 离子的混合配合物的合成及其结构和电子性质”Bull.Chem。日本社会学会.. 73・5。 1259-1275 (2000)