- 學位論文
取代基效應對含咪唑基之醯肼-腙衍生物的光致異構化及其金屬感測性質研究
Substituent effect on the photoisomerization of imidazole-containing hydrazine-hydrazone derivatives and their metal sensing properties
摘要
醯肼-腙衍生物在超分子化學、有機合成和藥物化學中扮演重要的角色，並已用於傳感器、分子開關、藥物以及其他應用。在本論文中我們合成三個以醯肼-腙為基礎之咪唑分子，分別為咪唑4,5位置上接有兩個苯環及氮上為甲基取代的分子4a、氮上為甲基取代的分子4b和4,5位置上接有兩個苯環及氮上為丙基取代的分子4c，探討咪唑分子上不同取代基對材料光物理性質的影響。 本篇我們會分成兩個部份來探討，第一部分是利用C=N的雙鍵結構進行光切換的實驗，研究不同取代基對於分子造成不同的光譜影響，以及在不同極性的溶劑下，經過光的刺激後，分子的光轉換速度，我們發現4a、4c在高極性的溶劑下分子光切換速度最快，4b則無明顯變化。第二部分則是研究分子與金屬的作用，我們加入數種不同的金屬離子，發現4a、4b、4c在吸收光譜上分子都有典型的MLCT的現象，以此證明分子與金屬的作用，特別是在加入汞離子的時候，會呈現明顯的粉紅色，其吸收及螢光光譜也會有所改變，由於4b的結構較小，較容易與金屬作用，在一當量時即可清楚的觀察到，反之，結構最大的4c在0.3當量才有些微的粉紅色產生，4b可以做為偵測汞金屬的金屬傳感器材料，未來在材料的應用方面有相當的潛力。
並列摘要
The hydrazide–hydrazone derivatives that play a significant role in supramolecular chemistry, organic synthesis as well as medicinal chemistry have been used in sensing, molecular switches, drugs and others. In this work, we synthesized three kinds of imidazole-containing hydrazine-hydrazone derivatives and investigated their physical properties, i.e. 1-methyl-4,5-diphenylimidazole-based molecule of 4a, 1-methyl-imidazole- based molecule of 4b and 1-propyl-4,5-diphenylimidazole- based molecule of 4c. This work will be divided into two parts. For the first part we used the C=N double bond to study the photoswitch properties of 4a-4c and would focused on the substituent effects as well as solvent effects. After light irradiation, we found that 4a and 4c have the fastest molecular light switching speeds in high-polar solvents, while 4b has no obvious change. The second part is to study the interaction between molecules and metals. We added several different kinds of metal ions and found that 4a, 4b, as well as 4c have typical MLCT phenomena in their absorption spectra, which proves the interaction between molecules and metals. Especially when mercury ions are added, it will appear obvious pink, and its absorption and fluorescence spectrum will also change. Since 4b has smaller structure, it is easier to interact with metals and can be clearly observed in one equivalent. On the contrary, 4c, which has the largest structure, is slightly pink at 0.3 equivalent. Therefore, 4b can be used as a metal sensor material for detecting mercury metal. It has considerable potential in material applications in the future.