Creation of organic redox systems exhibiting electrochemical switching for the development of unimolecular devices

创建具有电化学开关的有机氧化还原系统，用于单分子器件的开发

• 批准号: 14540486
• 负责人: ITO Shunji
• 金额: $ 2.3万
• 依托单位: Hirosaki University (2003-2004)Tohoku University (2002)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540486/
• 关键词: Unimolecular device; Organic redox system; Cyanine dye; Electrochromism; Cross-coupling reaction; Organometallics; π-Conjugated compound; Nonbenzenoidaromatics; 分子スイッチ; ディスコティック液晶

Creation of molecular devices has been examined utilizing the redox systems with one-electron transfer for the transmission of information. The low stability of the radical ionic state hampered the design of novel molecular devices. We applied the closed shell system produced by two-electron transfer for the improvement of the stability. We have prepared several responsive molecules by the concept of one-step two-electron transfer utilizing the azulene derivatives substituted by 2-or 6-positions, which were archived by the transition metal catalyzed reaction. The solubility of the compounds was improved by the introduction of octyl groups or hexyloxycarbonyl groups on the azulene rings. We have also prepared azulene derivatives with ethynyl spacers. The redox behavior of the novel π-conjugated compounds was examined by cyclic voltammetry. These compounds exhibited the presumed multiple electron transfer depending on the number of azulene rings. We anticipate that these new azulene derivatives should exhibit multiple color change depending on the redox state owing to the concept of cyanine-cyanine hybrid proposed by us recently. These compounds also exhibit liquid crystalline behavior in addition to the redox behavior. We also prepared p-phenylenediamines substituted by 6-azulenyl groups, which exhibited amphoteric redox behavior. Furthermore, we have developed novel organometallic reagents of azulenes and also revealed bond-length alternation on the 1-azulenylmethyl cations.

利用单电子转移的氧化还原系统来传输信息，已经研究了分子器件的创建。自由基离子态的低稳定性阻碍了新型分子器件的设计。为了提高稳定性，我们采用了由双电子转移产生的闭壳层体系。我们利用过渡金属催化的2位或6位取代的甘菊环衍生物，通过一步两电子转移的概念，制备了几种响应性分子。通过在甘菊环上引入辛基或己氧羰基，改善了化合物的溶解性。我们还制备了含乙炔基的甘菊环衍生物。用循环伏安法研究了这些化合物的氧化还原行为。这些化合物表现出假定的多重电子转移，这取决于奥林环的数量。由于我们最近提出的菁-菁杂化物的概念，我们预期这些新的甘菊环衍生物会呈现出多种颜色的变化，这取决于氧化还原状态。这些化合物除了氧化还原行为之外还表现出液晶行为。我们还制备了6-奥基取代的对苯二胺，它们具有两性氧化还原行为。此外，我们还开发了新的有机金属试剂的甘菊环，并揭示了1-甘菊环甲基阳离子的键长交替。

项目成果

アズレン環の特性を活かした有機機能性物質の創出

利用薁环的特性创造有机功能物质

• 发表时间: 2004
• 期刊: 有機合成化学協会誌 62・8
• 作者: S.Ito;M.Ando;A.Nomura;N.Morita;C.Kabuto;H.Mukai;K.Ohta;J.Kawakami;A.Yoshizawa;A.Tajiri;伊東 俊司;伊東 俊司;伊東 俊司
• 通讯作者: 伊東 俊司

伊東 俊司: "Synthesis, Stability, and Redox Behavior of Di(1-azulenyl)(6-azulenyl)methylium Hexafluorophosphates. Generation of a Donor-Acceptor Substituted Neutral Radical by Azulenes"The Journal of Organic Chemistry. 68・25. 9753-9762 (2003)

伊藤俊二：“二(1-薁基)(6-薁基)甲基鎓六氟磷酸盐的合成、稳定性和氧化还原行为。甘菊烯取代的供体-受体中性自由基的生成”有机化学杂志 68・25-。 9762 (2003)

Synthesis of poly(6-azulenylethynyl)benzene derivatives as a multielectron redox system with liquid crystalline behavior

• DOI: 10.1021/ja0209262
• 发表时间: 2003-02-12
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Ito, S;Inabe, H;Imafuku, K
• 通讯作者: Imafuku, K

Azulene-substituted aromatic amines. synthesis and amphoteric redox behavior of N,N-Di(6-azulenyl)-p-toluidine and N,N,N′,N′-tetra(6-azulenyl)-p-phenylenediamine and their derivatives

• DOI: 10.1021/jo048489s
• 发表时间: 2005-03-18
• 期刊: JOURNAL OF ORGANIC CHEMISTRY
• 影响因子: 3.6
• 作者: Ito, S;Kubo, T;Tajiri, A
• 通讯作者: Tajiri, A

Electrochromic Application of Enediyne Scaffolding as a Redox-Active Chromophore. Synthesis and Redox Behavior of 9,10-Bis[3-(6-azulenyl)-1-(6-azulenylethynyl)-2-propynylidene]- 9,10-dihydrroanthracenes

烯二炔支架作为氧化还原活性发色团的电致变色应用。

• 发表时间: 2004
• 期刊: European Journal of Organic Chemistry 8号
• 作者: S.Ito;M.Ando;A.Nomura;N.Morita;C.Kabuto;H.Mukai;K.Ohta;J.Kawakami;A.Yoshizawa;A.Tajiri;伊東 俊司;伊東 俊司
• 通讯作者: 伊東 俊司