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

从太阳能的有效利用角度来看，光合作用的人工复制是最具挑战性的课题之一。许多化学家都致力于提高电子转移的效率。本课题研究了一种新型的含联吡啶的杂环化合物的合成方法，并对其进行了功能评价.以对位取代苯甲醛为原料，经两步反应合成了一系列CA位带有对位取代苯的吡啶基吡啶酮。2.对吡啶基吡啶酮进行选择性O-烷基化，得到侧链带有氨基或羧基的2，27-联吡啶。3.新的2，2 '-联吡啶-钌配合物显示出与母体三（2，2'-联吡啶）钌（II）配合物相似的物理性质。4.采用分步偶联法合成了由L-鸟氨酸或L-赖氨酸、2，2 '-联吡啶、吩噻嗪和甲基紫精组成的杂合化合物。5.混合化合物-钌（II）络合物在MeCN中在460 nm附近显示出特征MLCT带。在Ar气氛下测量了钌配合物在水溶液中的发射寿命和发射量子产率。Phiem（ca. 0.0012）和燕鸥（约。25 ns）的光催化活性显著降低，表明该杂化化合物-钌（II）配合物可用于光催化剂，具有较高的电子转移效率。

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.