A Novel Synthesis of Bipyridine-Containing Hybrid Compounds Directed High Efficiency of the Electron Transfer and Their Functional Evaluation

光合作用的人工复制是太阳能有效利用中最具挑战性的主题之一。许多化学家致力于提高电子传递的效率。在本课题中，我研究了一种新的定向高效电子转移的含联吡啶杂化化合物的合成及其功能评价。以（对取代）苯甲醛为原料，经2步反应制得CA位含（对取代）苯的多种吡啶基吡啶酮。2. 吡啶基吡啶酮经选择性0-烷基化反应得到侧链上含氨基或羧基的2,27 -联吡啶。3. 新的2,2'-联吡啶-钌配合物与母体三（2,2'-联吡啶）钌（II）配合物具有相似的物理性质。4. 采用逐步偶联的方法合成了由l -鸟氨酸或l -赖氨酸、2,2′-联吡啶、吩噻嗪和甲基紫酮组成的杂化化合物。5. 杂化化合物-钌（II）配合物在MeCN.6中显示出460 nm左右的特征性MLCT波段。测定了钌配合物在水溶液中氩气氛下的发射寿命和发射量子产率。与母体三（2,2′-联吡啶）钌配合物相比，PHIem（约0.0012）和tern（约25 ns）显著降低。综上所述，该杂化化合物钌（II）配合物具有较高的电子转移效率，可用于光催化剂。

The artificial duplication of photosynthesis is one of most challenging themes in a viewpoint of the efficient utilization of solar energy. Many chemists have focused on improvement of the efficiency of the electron transfer. In this project, I investigated a novel synthesis of bipyridine-containing hybrid compounds directed high efficiency of the electron transfer and their functional evaluation.1. A variety of pyridylpyridones bearing (p-substituted)benzene at CA position were prepared from (p-substituted)benzaldehydes via 2 steps. 2. Pyridylpyridones were subjected to the selective 0-alkylation to afford 2, 27-bipyridines bearing amino or carboxyl group at the side chain. 3. New 2, 2'-bipyridine-ruthenium complexes showed similar physical properties to the parent tris(2,2'-bipyridme)ruthenium(II) complex. 4. Hybrid compounds composed of L-ornithine or L-lysine, 2,2'-bipyridine, phenothiazine, and methyl viologen were synthesized using the stepwise coupling. 5. Hybrid compound-ruthenium(II) complexes showed characteristic MLCT bands around at 460 nm in MeCN.6. Emission life times and emission quantum yields of ruthenium complexes were measured in aqueous solutions under Ar atmosphere. PHIem (ca. 0.0012) and tern (ca. 25 ns) were dramatically decreased compared with the parent tris(2,2'-bipyridine)ruthenium complex.In conclusion, the present hybrid compound-ruthenium(II) complexes were demonstrated to be applicable to photocatalysts which showed high efficiency of the electron transfer.