本論文中使用靜態螢光光譜儀、紫外線-可見光吸收光譜儀及時間相關單光子計數器(TCSPC)研究4-苯胺基反式雙苯乙烯及其衍生物(trans-4-(N-arylamino)stilbenes,p1CN及p1OM)之環境侷限研究效應。我們使用溴化十六烷基三甲銨(CTAB)及十二烷基硫酸鈉(SDS)作為界面活性劑，將目標分子以及溶劑溶解在水中，並且形成微胞，並利用濃度的控制使得每個微胞中只有一個目標分子。目標分子在CTAB微胞中之吸收及放光光譜一致性非常高，但卻又與單純在溶劑中不同，推測在微胞的環境下，分子的行為是非常相近的，不受微胞中之溶劑影響。苯胺基雙苯乙烯及其衍生物經375 nm光激發，以TCSPC觀測其螢光衰減及生命期，發現到在溶劑中有兩個生命期，p1CN的τ1為 <0.06 ns~0.25 ns，τ2為1.6~2.6 ns，而p1OM的τ1為 <0.06 ns~0.53 ns，τ2為0.6~2.3 ns，其生命期與溶劑之極性與特性有關，而目標分子在有微胞的環境下，生命期卻非常的一致，不論是p1CN或是p1OM，兩者之τ1與τ2約為0.1 ns及0.5 ns，與靜態光譜得到結果相比較，可得知在微胞環境下之放光環境相似。我們推測在CTAB中，其中的四級銨鹽會與目標分子中之苯環形成n-pi 鍵結，導致其生命期以及靜態光譜之結果非常類似，並不受溶劑影響。而在十二烷基硫酸鈉中，加入各溶劑後生命期也很相近，於p1CN觀察到三種不同的生命期，分別為 τ1 <0.06 ns及τ2 = 0.10±0.02 ns與τ3 = 0.30±0.11，而p1OM 只有觀察到兩種生命期，τ1與τ2約為0.1 ns及0.5 ns，我們推測在SDS環境中，p1CN以及p1OM會與SDS分子形成不一樣的氫鍵結構，造成有兩種不同的分子內電荷轉移結構，但是p1OM在丁腈於微胞中呈現不一樣的現象，並且在靜態光譜也不一樣，其放光優於在其他溶劑中，推測p1OM在丁腈於微胞之構型與其他不同，可能部份分子是存在於微胞中心的溶劑內。

We use fluorescence spectra, uv-vis spectra and time-correlated single photon counting(TCSPC) to investigate environmental confinement effects of trans-4-(N-arylamino)stilbenes(p1CN and p1OM). We use CTAB and SDS as the surfactants to dissolve p1CN, p1OM and organic solvent in water and form the micelles, we use concentration to control that there is only one molecule in each micelle. Target molecules, which dissolve in CTAB solution, show the same properties in fluorescence spectra and uv-vis spectra, but different from dissolve in organic solvent, we assume that molecules’ behavior are very closely and without influence of the solvent we add. We excite trans-4-(N-arylamino)stilbenes with 375 nm laser beam, using TCSPC to observe fluorescence lifetime. There are two different lifetime, p1CN’s τ1 is about <0.06 ns~0.53 ns and τ2 is about 0.6~2.3 ns, p1OM’s τ1 is about <0.06 ns~0.53 ns and τ2 is about 0.6~2.3 ns. In CTAB solution, p1CN and p1OM have the same fluorescence lifetime which τ1 = 0.1 ns and τ2 = 0.5 ns, we surmise that the phenyl group in our molecules would have cation-pi interaction with tetramethylammonium ion in CTAB. In SDS solution, the fluorescence lifetime are very similar, too. We found three different lifetime in p1CN, τ1 <0.06 ns, τ2 = 0.10±0.02 ns and τ3 = 0.30±0.11, in p1OM, we only observed two kinds of lifetime, τ1 is about 0.1 ns and τ2 is about 0.5 ns, we assume that p1CN and p1OM would form two kinds of H-bond, which cause two kinds of intramolecule charge transfer, but p1OM-BuCN-SDS showed different properties from others, p1OM might exist at the center of the micelle.

第一章 序論 1
1.1 前言 1
1.2 文獻回顧 1
1.2.1 反式雙苯乙烯與推拉電子系統介紹 1
1.2.2 反式-胺基雙苯乙烯(trans-aminostilbene)及目標分子簡介 5
1.2.3 溴化十六烷基三甲銨 11
1.2.4 cation-pi 鍵結系統 11
1.2.5 重疊效應(stacking) 13
1.2.6 十二烷基硫酸鈉 13
1.3 研究動機 14
第二章 實驗方法及儀器架設 15
2.1 靜態吸收與螢光光譜儀 15
2.2 時間相關單一光子計數器(time-correlated single photon counting, TCSPC) 15
2.3 動態光散射儀 (Dynamic light scattering, DLS) 19
2.4 實驗樣品配置方法 19
第三章 實驗數據及結果 21
3.1 微胞尺寸鑑定 21
3.2 p1CN 22
3.2.1 靜態吸收以及螢光光譜結果 22
3.2.2 時間相關單光子計數器 23
3.3 p1OM 25
3.3.1 靜態吸收以及螢光光譜結果 25
3.3.2 時間相關單光子計數器 26
第四章 討論 70
4.1 反式對位苯胺基雙苯乙烯衍生物之CTAB以及SDS微胞溶液 70
4.2 動力學模型之討論 70
4.2.1 p1CN 70
4.2.2 p1OM 75
4.2.3 在CTAB及SDS中p1CN與p1OM的TICT行為 79
第五章 結論 100

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