Syntheses of New Multifunctional Viologen Derivatives and their Application for New Materials

新型多功能紫罗碱衍生物的合成及其新材料应用

• 批准号: 63550679
• 负责人: ENDO Takeshi
• 金额: $ 1.22万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63550679/
• 关键词: Multifunctionality; Viologen; Dihydronicotinamide; Crown Ether; Azobenzene; Benzophenone; Charge Transfer Complex; Intramolecular Electron Relay; ジヒドロニコチンアミド; 分子内電子移動; ビニルビオロゲン; ビルルアゾベンゼン

We investigated In this research the syntheses and application of new multi-electron transfer systems related to the well-known redox function, viologen and their development to polymeric systems.As new multi-electron transfer systems, we synthesized viologen derivatives bearing azobenzene, substituted benzophenones, dihydronicotinamidet or crown ethers linked with various spacers.In these new systems, we could find some new behaviors based on the intramolecular interactions between functional groups, which were not observed between the corresponding intramolecular systems.In the viologen derivatives having substituted benzophenone or dihydro- nicatinamide structure, charge transfer complexation between these functional groups were observed. In these systems, the photoinduced electron relay were observed in the aprotic medium for the first time.By the comparison of the redox behaviors in the viologen derivatives having the azobenzene structure with various linkages, the electron relay in both groups was found to be most effective, when these groups were connected with propylene linkage due to the stacked conformation of both groups. In this case the direction of electron relay was controlled by pHs.In the viologen derivative having the crown ether structure, the Na_2S_2O_4 reduction of vialogen part was accelerated by the crown ether part in the mixed solvent of water and acetonitrile.In order to introduce the above-mentioned multi-electron transfer systems in the polymer, some new monomers were synthesized which have vinyl groups directly linked to the functional groups. and the copolymers were synthesized with the viologen and other functional groups having as direct pendants. In these copolymers, charge transfer complexation,and intramolecular electron transfer were also observed much extensively than those in the monomeric model systems.

本论文研究了与氧化还原功能有关的新型多电子转移体系--紫精的合成和应用及其在聚合物体系中的发展.作为新型多电子转移体系，我们合成了偶氮苯、取代二苯甲酮、二氢烟酰胺或冠醚等与不同间隔基相连的紫精衍生物.在这些新体系中，在具有取代二苯甲酮或二氢烟酰胺结构的紫精衍生物中，观察到了官能团间的电荷转移络合作用。通过比较不同连接方式的偶氮苯结构紫精衍生物的氧化还原行为，发现当偶氮苯结构的紫精衍生物与丙烯连接时，由于两个基团的堆积构象，两个基团中的电子传递最有效。具有冠醚结构的紫精衍生物在水和乙腈的混合溶剂中，冠醚部分加速了Na_2S_2O_4还原紫精部分，为了在聚合物中引入上述多电子传递体系，在水和乙腈的混合溶剂中，冠醚部分的存在促进了Na_2S_2O_4还原紫精部分。合成了一些新的单体，其具有直接连接到官能团的乙烯基。并且以紫精和其它官能团作为直接侧基合成共聚物。在这些共聚物中，电荷转移络合，和分子内电子转移也观察到更广泛的比那些在单体模型系统。

项目成果

Yoko Nambu: "First Observation of an Intramolecular Charge Transfer and Electron Relay between the Viologen and Ester Groups in a New Copolymer System" Macromolecules. 22. 3530-3532 (1989)

Yoko Nambu：“首次观察到新共聚物体系中紫罗碱和酯基团之间的分子内电荷转移和电子中继”大分子。

Takeshi Endo and Toshikazu Takata: "Syntheses of Multifunctionalized Polymers" Kobunshi, 37(9), 662-665 (1988).

Takeshi Endo 和 Toshikazu Takata：“多功能聚合物的合成”Kobunshi，37(9), 662-665 (1988)。

Naoya Kitamura: "Preparation of a Polymeric Membrane Crosslinked by the Viologen Structure from a Cyanopyridinium Salt Polymer" J.Polym.Sci.,Polym.Chem.Ed.26. 992-1001 (1988)

Naoya Kitamura：“由氰基吡啶鎓盐聚合物通过紫精结构交联的聚合物膜的制备”J.Polym.Sci.，Polym.Chem.Ed.26。

Toshihiko Sato: "Incorporation of Viologen Moiety as Redox Function into Hydroxypropyl Cellulose" J.Polym.Sci.,Polym.Lett.Ed.28. 289-292 (1989)

Toshihiko Sato：“将紫罗碱部分作为氧化还原功能掺入羟丙基纤维素中”J.Polym.Sci.，Polym.Lett.Ed.28。

Takeshi Endo: "Synthesis of Polyethers Containing Viologen Moiety and Their Application to Electron Transfer Catalyst" J.Polym.Sci.,Polym.Chem.Ed.in press.

Takeshi Endo：“含有紫罗碱部分的聚醚的合成及其在电子转移催化剂中的应用”J.Polym.Sci.，Polym.Chem.Ed.in press。