| 摘要: | 中文摘要 本論文乃延伸先前本實驗室對反式-4-N-芳基二苯乙烯胺化合物(1-OMe、1-Me、1-H、1-Cl、1-CF3、1-CO2Me、1-CN)的激發態行為之研究。在高極性溶劑中，其1-OMe、1-CN和1-CO2Me被認為具有TICT態，則其他四個則不具TICT態。我們於是合成相關衍生物來進一步的研究此TICT態的結構和螢光性質。 在探討化合物1-OMe、1-CO2Me和1-CN的TICT態方面，我們合成架橋化合物3、4、5和6來作比較。其螢光光譜圖、量子產率等螢光行為我們推斷1-CN的TICT態的單鍵扭轉位置在苄腈基和氮二苯乙烯基間的單鍵，而1-OMe的TICT態的單鍵扭轉位置在二苯乙烯基和苯胺基間的單鍵。 在探討無TICT態的化合物1-H，我們由化合物AS、DS、1-H和1-DPhS與化合物6-AS、6-DS、6-H和6-DPhS在正己烷的螢光光譜的振動(0,0)峯和(0,1)峯分析可知此類化合物的振動光譜最主要是受構形效應的影響而由(0,0)峯和(0,1)峯比值的變化顯示這系列化合物在正己烷中的激發態結構是平面性的。當我們改變溶劑的極性，由螢光最大放射峯的能量與溶劑極性ET(30)參數間的線性關係顯示這系列的化合物在極性溶劑中發螢光的激發態亦是平面性結構。 Abstract This thesis presents our complimentary studies on the excited state behavior of trans-4-(N-arylamino)stilbenes 1-OMe, 1-Me, 1-H, 1-Cl, 1-CF3, 1-CO2Me, and 1-CN. The previous work carried out in our laboratory on these aminostilbenes has suggested that there is a TICT state for 1-OMe, 1-CN, and 1-CO2Me but not for the other four species in polar solvents. We have thus synthesized a series of related compounds to clarify the structures and the fluorescence behavior of these TICT states. In this context, the ring-bridged compounds 3-6 have been prepared and compared with compounds 1. The results suggested that the TICT states for 1-CN and 1-CO2Me result from the twisting of the anilino-benzonitrilo C-N bond and that it is from the twisting of the stilbenyl-anilino C-N bond for 1-OMe. We have also analyzed the fluorescence vibronic structures of a series of aminostilbenes in hexane. They are AS, DS, 1-H, 1-DPhS, 6-AS, 6-DS, 6-H, and 6-DPhS. According to the relative intensity of the 0-0 vs 0-1 band, we concluded that the observed N-substituent effect on the vibronic structure is mainly due to the conformational perturbation on the geometry of the amino group. In addition, it is consistent with a planar fluorescing ICT state for these aminostilbenes in hexane. A linear correlation between the fluorescence peak energy and the solvent polarity parameter Et(30) indicates that the fluorescing states of these aminostilbenes are also planar in polar solvent. |
