Synthesis and properties of ethylene-, vinylene-, and diacetylene-groups connected porphyrin hexamer

亚乙基、亚乙烯基和联乙炔基连接的卟啉六聚体的合成与性能

• 批准号: 18550029
• 负责人: HIGUCHI Hiroyuki
• 金额: $ 2.62万
• 依托单位: University of Toyama
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18550029/
• 关键词: porphyrin; ethylene; vinylene; diacetylene; electronic property; hexamer; nano-size; coupling; 電子吸収スペクトル; 核磁気共鳴スペクトル; 四量体; ポルフィリン

Oligornerization of the pai-electronic conjugated cyclic system which have wide area and thus highly respond to outside stimulations is a very important methodology for the development of new functional organic materials. Among the pai-electronic conjugated cyclic systems, porphyrin ring system is particularly promising as seen in an example of a special dimer in a photo-synthesis reaction center. Therefore, oligomerization of porphyrin ring with various linkages has been demonstrated to achieve a wide variety of purposive functions such as photocurrent (PC) and electroluminescence (EL). We also previously reported the synthesis of vinylene-group connected octaethylporphyrin trimer, (OEP)3, and studied its electronic property, proving that the electron releasing ability, for instance, outstandingly enhances in order of (OEP) <<(OEP) 2 <<<(OEP)3.Successively to this result, in the present research stint, dimerization of the (OEP)3 component by connecting with ethylene linkage was planne … More d in cider to examine the electronic properties of ethylene- and vinylene-groups connected OEP hexamer, (OEP)6. After several examinations, we were successful in introducing the functional groups such as formyl (CHO) and alcohol (CH2OH) onto the central OEP ring of (OEP)3 selectively. And, both Mcmurry coupling of the CHO derivative and acid-catalyzed coupling of the CH2OH derivative were examined to lead to the corresponding (OEP)6 derivatives. From the former reaction, the all-vinylene-group cannected (OEP)6 derivative was not obtained at all, only affording the insoluble materials. On the other hand, from the latter reaction, the ethylene- and vinylene-groups connected (OEP)6 derivative was successfully isolated, the molecular structure of which was fully determined by means of MS, PMR and electronic absorption spectra. It was proved that the present (OEP)6 derivative substantially possesses the electronic properties of the vinylene-group connected (OEP)3 derivative and thus is regarded as a dime is structure of the vinylene-group connected (OEP)3 simply connected with ethylene linkage.On the way of the present research, an unsymmetrical molecular motion was observed in the CHO and CH2OH derivatives of vinylene-group connected (OEP)3, probably due to the steric repulsion between those substituents and the peripheral ethyl substituents. In other words, these (OEP)3 derivatives were found to possess the unsymmetric molecular structure at room temperature, where both three OEP rings and two vinylene linkages are different from each other, respectively.Furthermore, in relation with these properties of oligomeric (OEP)n derivatives, the diacetylene- and ethylene-group connected (OEP)4 derivative with symmetrical molecular structure has been preliminarily proved to be a host molecule which forms inclusion complexes with various guest molecules. If a guest molecule has a chirality, such an inclusion complex should be chiral. In practice, the diacetylene- and ethylene-group connected (OEP)4 derivative showed an active circuler dichroism (CD) spectral behavior, by forming the corresponding inclusion complexes with optically active substances like (R)- or (S)-2-alkanols. Thus, at present, the preparation of a large quantity of the ethylene-and vinylene-group connected (OEP)6 derivatives is underway to examine its CD spectral behavior. Less

双电子共轭环体系的低聚化是开发新型功能有机材料的一种重要方法。在对电子共轭环体系中，卟啉环体系在光合反应中心的特殊二聚体的例子中尤其有前景。因此，具有各种键的卟啉环的寡聚化已被证明可以实现各种各样的目的功能，如光电流（PC）和电致发光（EL）。我们之前也报道了乙烯基连接的八乙基卟啉三聚体（OEP）3的合成，并对其电子性质进行了研究，证明其电子释放能力，如(OEP) <<(OEP) 2 <<<(OEP)3的顺序显著增强。在此基础上，本研究进一步研究了OEP六聚体（OEP）6的乙烯基团和乙烯基团的二聚化反应。经过多次试验，我们成功地将甲酰（CHO）和醇（CH2OH）等官能团选择性地引入到（OEP）3的OEP中央环上。并对CHO衍生物的Mcmurry偶联和CH2OH衍生物的酸催化偶联进行了研究，得到了相应的（OEP）6衍生物。在前一反应中，没有得到全乙烯基连接（OEP）6衍生物，只得到不溶性物质。另一方面，从后一反应中成功分离出乙烯基和乙烯基连接（OEP）6衍生物，并通过质谱、PMR和电子吸收光谱对其分子结构进行了充分的测定。证明了该（OEP）6衍生物实质上具有乙烯基连接（OEP）3衍生物的电子性质，因此可视为乙烯基连接（OEP）3的单键连接结构。在本研究的过程中，在乙烯基连接（OEP）3的CHO和CH2OH衍生物中观察到不对称的分子运动，可能是由于这些取代基与周围的乙基取代基之间的空间排斥作用。换句话说，这些（OEP）3衍生物在室温下具有不对称的分子结构，其中三个OEP环和两个乙烯键分别不同。此外，根据低聚物（OEP）n衍生物的这些性质，初步证明具有对称分子结构的二乙炔和乙烯基连接（OEP）4衍生物是与各种客体分子形成包合物的宿主分子。如果客体分子具有手性，那么这种包合物应该是手性的。在实践中，二乙炔和乙烯基连接（OEP）4衍生物通过与(R)-或(S)-2-烷醇等光学活性物质形成相应的包合物，表现出积极的环状二色性（CD）光谱行为。因此，目前，大量乙烯基和乙烯基连接（OEP）6衍生物的制备正在进行中，以研究其CD光谱行为。少

项目成果

Orientation and Substituent Effects on the Properties of the Diacetylene-Group Connected Octaethylporphyrin-Dihexylbithiophene Derivatives (OEP-DHBTh-X) Carrying Electron-Withdrawing Groups

• DOI: 10.1246/bcsj.80.371
• 发表时间: 2007-02
• 期刊: Bulletin of the Chemical Society of Japan
• 影响因子: 4
• 作者: N. Hayashi;Takashi Nishihara;Takuya Matsukihira;H. Nakashima;K. Miyabayashi;M. Miyake;H. Higuchi

Synthesis, Structure, and Properties of Benzoquinone Dimer and Trimers Bearing t-Bu Substituents

带有叔丁基取代基的苯醌二聚体和三聚体的合成、结构和性能

• 发表时间: 2007
• 期刊: Org. Lett. 9
• 作者: 鈴木崇将;高橋雅樹;依田秀実;N.Hayashi
• 通讯作者: N.Hayashi

Synthesis and Properties of the Octaethylporphyrin -dihexylbithiophene-Pyridine System (OEP-DHBTh-Py) Connected with Diacetylene Linkage. Proton-mediated and Heat-driven Spectral Changes.

联乙炔键连接的八乙基卟啉-二己基联噻吩-吡啶体系（OEP-DHBTh-Py）的合成和性能。

• 发表时间: 2006
• 期刊: Tetrahedron Lett. 47
• 作者: Hayashi;N.;Matsukihira;T;Miyabayashi;K.;Miyake;M.;Higuchi;H.
• 通讯作者: H.

Synthesis and Electronic Properies of Dimeric Octaethylporphyrin(OEP)Derivatives Spaced with p-Phenylene Group [OEP-(p-Phen)n-OEP].A comparative Study with Dihexylbithiophene(DHBTh)Group-Spaced OEP Dimers[OEP-(DHBTh)n-OEP]

对亚苯基二聚八乙基卟啉(OEP)衍生物[OEP-(p-Phen)n-OEP]的合成及电子性质。与二己基联噻吩(DHBTh)基团OEP二聚体[OEP-(DHBTh)n的比较研究

• 发表时间: 2007
• 期刊: Sci.Tec.Adv.Mat. 8
• 作者: N;Hayashi.;and H;Higuchi;宮前孝行;N. Hayashi;T. Miyamae;T.Miyamae;N. Hayashi
• 通讯作者: N. Hayashi

Synthesis and Electronic Properties of Dimeric Octaethylporphyrin (OEP) Derivatives Spaced with p-Phenylene Group [OEP-(p-Phen)n-OEP]. A Comparative Study with Dihexylbithiophene (DHBTh) Group-Spaced OEP Dimers |OEP-(DHBTh)n-OEP

对亚苯基二聚八乙基卟啉 (OEP) 衍生物的合成和电子性质 [OEP-(p-Phen)n-OEP]。

• 期刊: Sci. Tec. Adv. Mat. (in press)
• 作者: H.Benten;H.Ohkita;S.Ito;M.Yamamoto;Y.Tohda;K.;Hiroaki Benten;Hiroaki Benten;Hiroaki Benten;Naoto Hayashi;N.Hayashi
• 通讯作者: N.Hayashi