【作者】 孙辉；

【导师】 王梅；

【作者基本信息】 大连理工大学 ， 有机化学， 2011， 硕士

【摘要】 设计合成了含三苯胺和吡啶官能团的光敏化合物作为分子器件的光捕获单元,通过紫外光谱证明了光敏化合物的吡啶官能团与钴肟配合物的配位相互作用,由此构建了基于钴肟配合物的光活性分子器件。利用MS和1HNMR对所合成的光敏化合物和分子器件的结构进行了表征,研究了分子器件的紫外、荧光、电化学及光致产氢性质。根据分子器件和三乙胺的氧化还原电位,以及分子器件中光敏化合物的荧光淬灭现象,从光敏单元向钴肟配合物的分子内电子转移是热力学可行的,但在光致产氢实验中未检测到氢气。可能是由于分子器件电荷分离态寿命短,电子回传速度快所致。论文还设计合成了两个能够传输空穴的带有三苯胺和邻菲罗啉官能团的配体L1和L2(L1=4-[4-((4-(1H-咪唑[4,5-f][1,10]邻菲罗啉-2-位)苯基)(苯基)氨基)苯基]-苯甲酸,L2=4-[(4-(1H-咪唑[4，5-f][1,10]邻菲罗啉-2-位)苯基)(苯基)氨基]苯基亚磷酸二乙酯)。L1和L2配体分别与[Ru(bpy)2Cl2]反应生成光敏剂(1)和(2)。两个配体上分别引入了能够吸附在p型半导体材料上的羧基和磷酸基,期望利用p型半导NiO向光致放氢体系提供电子,而不需要外加牺牲电子给体。利用MS和1HNMR对所合成的配体和光敏剂的结构进行了表征,研究了光敏剂的荧光、紫外、电化学及瞬态吸收光谱。测试结果表明光诱导光敏剂到电子载体(MV2+)的电子转移和由此引发在光敏剂内部的空穴传输是可行的。更多还原

【Abstract】 A photosensitizer containing triphenylamine and pyridine functional group was designed and synthesized as a light capturing unit for a molecular device. An axial coordination of the pyridine group of the photosensitizer to a cobaloxime complex results in construction of a new noble-metal-free molecular device. The structures of the photosensitizer and the molecular device were characterized by MS and1H NMR spectroscopy. The UV-vis and fluorescence spectra, electrochemistry of the molecular device, and photoinduced hydrogen production with the device were studied. On the basis of the apparent quenching of the fluorescence emission in the molecular device as compared to that of the free photosensitizer and the redox potentials of the molecular device, photosensitizer, and triethylamine, the intramolecular photoinduced electron transfer from the photosensitizer unit to the cobaloxime unit is thermodynamically feasible. But no H2 was detected by GC analysis in the photocatalytic reaction with the molecular device, presumably due to fast electron recombination and/or a short life of charge-separated state of the molecular device.Two lignds containing triphenylamine and phenanthroline functional group were prepared (L1=4-[4-((4-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenyl)(phenyl)amino) phenyl]-benzoic acid, L2=4-[(4-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenyl) (phenyl)amino]-phenylphosphonic acid diethyl ester). Coordination of the ligands to [Ru(bpy)2Cl2] results in construction of two new photosensitizers. The structures of the ligands and photosensitizers were characterized by MS and1H NMR spectroscopy. The UV-vis and fluorescence spectra, as well as electrochemistry of photosensitizers were studied. The electron transfer was verified by transient absorption spectroscopy and kinetic traces obtained from laser flash photolysis.更多还原