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標題: 紫質與三芳香胺之共軛合成
Synthesis of porphyrin and triarylamine conjugates
作者: 馬啟顓
關鍵字: porphyrin;紫質;triarylamine;conjugates;Pd-coupling;TiO2 solar cell;三芳香胺;共軛合成;太陽能電池原料
出版社: 化學系
在此論文主要討論帶有三鍵的鋅金屬紫質與三芳香胺的合成,以鈀錯合物做催化劑,將meso位置含有碳-碳三鍵之紫質與帶有官能基碘的三芳香胺行偶合反應,並得到高的產率,另對此化合物做性質上的探討。在電子吸收光譜上,我們發現此化合物與meso四芳香族取代紫質比較,有著紅光偏移與強而寬的Q band吸收,螢光光譜顯示紫質與三芳香胺有著能量傳遞的情形,而透過X光繞射的結晶結構可以發現此分子呈現近乎平面的形狀,三鍵與立體結構提供了紫質與三芳香胺的高共軛性,最重要的是在電化學循環伏安法發現此分子有四對的氧化,第一與第二對可逆的氧化我們視為紫質上的反應,第三與第四對氧化相隔大約30mV,歸類於三芳香胺的部分。我們把此歸因為兩個三芳香胺能透過紫質在大於2奈米的距離下互相偶合,另一方面討論的是在三芳香胺終端上接上不同的取代基,並觀察取代基對性質的影響。最後,合成出在以三鍵連接鋅紫質的苯環上放上酸基,討論可能發展成為太陽能電池原料的潛力。

A set of porphyrin-triarylamine hybrids have been synthesized by Sonogashira palladium-catalyzed cross-couplingreaction between 5,15-diethynyl-10,20-dimestitylporphyrin and the appropriate iodophenyldiarylamine in a fair or good yield. The X-ray crystal structure of one of these conjugates is presented. The electronic spectra are red-shifted and display a broad Soret band and an intense Q band relative to those of meso-substituted tetraarylporphyrins. The fluorescence spectra display the energy transfer between porphyrin and triarylamine. These conjugates display four oxidation. The first and second oxidations are reversible and can be assigned to the the porphyrin-centered reactions. The thired and fourth ones, separated by about 300mV, correspond to the triarylamine units. The electron coupling between the triarylamine moieties is remarkable strong as we consider the remote distance over 2.0 nm. The electrochemical results and the absorption spectra show that the electronic characteristics of these porphyrins can be significantly modulated by the triarylamine substituents via the conjugated corbon-carbon triple bond. The variations of the substituents on the triarylamine can fine-tune the electronic properties of these molecules. Another, The compound acid group attach to the phenyl position of the compound Zn(Ⅱ) [5,15-Bis(phenylethynyl)-10,20-dimesitylporphyrin] have been synthesized, it may regard as the material for solar cell.
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