| Summary: | 碩士 === 國立中央大學 === 化學研究所 === 97 === The purpose of this research is to synthesize novel molecular dyes that possess a potential of applying on the fabrication of dye-sensitized solar cells. Synthesis and
spectroscopic characterization of asymmetric free-base thisaporphyrins that are attached by various numbers of carboxylic acid and electron donating groups, 10-(4-carboxyphenyl)-5,15,20-tris(p-tolyl)-21-monothiaporphyrin (8),10,15-bis(4-carboxyphenyl)-5,20-bis(p-tolyl)-21-monothiaporphyrin (9), 5,10,15,20-tetra(4-carboxyphenyl)-21-thiaporphyrin (13), and 10,15-bis(4-carboxyphenyl)-5,20-bis(3,4,5-trimethoxyphenyl)-21-mono-thiaporphyrin (19), have been achieved. Moreover, the first zinc(II) thiaporphyrin complex (20) has also been successfully prepared, and the structural characterization was unambiguously corroborated with single-crystal X-ray diffraction analysis. From the measured result of solar energy to electricity conversion efficiency (η), the h values are 0.11, 0.07, 0.06, and 0.12% for compounds 8, 9, 13, and 19, respectively. With introduction of electron donating groups, 3,4,5-trimethoxylphenyl, into the skeleton of thiaporphyrin 9, the push-and-pull functional thiaporphyrin molecule (19) can be highly promoted ca. 71% on η value. By means of modification with push-and-pull
and steric crowded groups, the possibility of molecular aggregation as well as charge recombination could be decreased, i.e. the electronic communication between a
molecular dye and the conductive band of TiO2 could be improved. On the other hand, zinc metallation of thiaporphyrin molecules has been directly carried out on the surface of TiO2 film, which was attached by thiaporphyrin molecules, by monitoring the shift on the Uv-vis spectrum.
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