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.

已经使用具有单电子传输的氧化还原系统来检查分子设备的创建。自由基离子状态的低稳定性阻碍了新型分子装置的设计。我们应用了由两电子转移产生的封闭壳系统，以提高稳定性。我们已经通过使用2或6位取代的替代衍生物的一步两电子转移的概念制备了几个响应性分子，这些替代衍生物由2或6位取代，这些衍生物由过渡金属催化的反应存档。通过在叠氮环上引入八氧基基团或己氧化碳苯子基团，可以提高化合物的溶解度。我们还用乙基垫片制备了叠氮衍生物。通过环状伏安法检查了新型π共轭化合物的氧化还原行为。这些化合物表现出假定的多电子转移，具体取决于叠氮环的数量。我们预计，由于最近我们提出的氰氨酸 - 氰胺混合动力的概念，这些新的叠素衍生物应根据氧化还原状态表现出多种颜色变化。除氧化还原行为外，这些化合物还表现出液晶行为。我们还制备了由6-氮苯基群取代的p-苯基二甲酰胺，该基苯基暴露了两性氧化还原行为。此外，我们已经开发了新型的Azulenes有机试剂，并且还揭示了1-余酰甲基阳离子的键长替代品。

项目成果

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)

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

Creation of advanced materials taking full advantage of azulene skeleton

充分利用甘菊骨架创造先进材料

• 发表时间: 2004
• 期刊: Journal of Synthetic Chemistry 62(8)
• 作者: S.Ito;N.Morita;T.Kubo
• 通讯作者: T.Kubo

Synthesis, Stability and Bonding Situation of Tris-, Bis- and Mono[9-(azuleno-[1,2-b]thienyl)Jmethyl Cations

三-、双-和单[9-(azuleno-[1,2-b]噻吩基)J甲基阳离子的合成、稳定性和键合情况

• 发表时间: 2003
• 期刊: Organic & Biomolecular Chemistry 1・14
• 作者: S.Ito;T.Terazono;T.Kubo;T.Okujima;N.Morita;T.Murafuji;Y.Sugihara;K.Fujimori;J.Kawakami;A.Tajiri;伊東 俊司;伊東 俊司;伊東 俊司
• 通讯作者: 伊東 俊司

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