吾人以時間相關單光子計數系統研究兩種以矽烷基作為間隙物之光引誘電子傳遞共聚物單體DA與DAD，給體D為苯胺，受體A為反式雙苯乙烯，給體與受體之間以矽烷基 (SiMe2) 做為橋樑。以波長266 nm之飛秒雷射為激發光源，在非極性溶劑中偵測局部激發至給體與受體激發態的放光，以兩個自然指數衰減，分別指認為受體之構型緩解生命期τi (85~140 ps)以及受體和給體第一激發態的螢光生命期τ0 (1、4 ns)。在中等極性的溶劑中，偵測局部激發給體與受體激發態的放光，放光以三個自然指數衰減，分別指認為生成電子轉移態的生命期τLE→CT (0.5~3 ps)、受體構型緩解生命期τi (70~210 ps)以及受體和給體第一激發態的螢光生命期τ0 (1~4 ns)。偵測電荷分離態的放光所適解出的生命期，分別為時間零點處為一個極短的上升生命期，可對應至電荷分離態生成的生命期τLE→CT (0.5~3 ps)、一個較短的衰減生命期τDecay (100~150 ps)和稍長的上升生命期(150~200 ps)為涉及構型轉變之不同電荷轉移態生成之生命期，最長的衰減生命期為電荷重合的生命期τRECT(4~5.5 ns)。本論文研究結果顯示DA及DAD兩分子受光激發後在極性環境中能進行相當有效率的電荷轉移，很適合應用於光引誘電子傳遞材料。

We used time-correlated single photon counting to investigate two photoinduced electron transfer dialkylsilylene-spaced donor-acceptor oligomers DA and DAD. The aniline is the electron Donor (D), trans-stilbene is the electron Acceptor (A) and SiMe2 as a spacer. We excited DA and DAD with a 266 nm laser beam. In non-polar solvents only the locally excited State (LE state) emits.The observed lifetimes, arranged from short to long are assigned to, the isomerization lifetime of trans-stilbene (τi) around 80-150 ps and the acceptor and donor fluorescence lifetime (τ0) are 1 ns and 4 ns. In slightly polar solvents, the LE state emission band displays three exponential decay. The observed lifetimes, arranged from short to long are assigned to, the formation of the charge transfer state lifetime (τLE→CT) is around 0.5-3 ps, the isomerization lifetime of trans-stilbene (τi) is around 70-210 ps and the acceptor and donor fluorescence lifetime (τ0) are 1 and 4 ns. In polar solvents, we detect the charge transfer state (CT state) emission. The observed lifetimes, arranged from short to long are assigned to, the lifetime of the formation of charge transfer state (τLE→CT) is ultrashort at zero timing, the decay lifetime (τDecay) is around 100-150 ps, the rise lifetime (τRise) is around 150-200 ps and the charge recombination lifetime (τRECT) is around 4-5.5 ns. τDecay and τRise are corresponding to the formation of the different intramolecular charge transfer states (ICT states) lifetimes. The experimental results imply the efficient charge transfer of DA and DAD in polar environments. DA and DAD are suitable for using in photoinduced electron transfer materials.

摘要
ABSTRACT II
謝誌 III
目錄 IV
表目錄 VI
圖目錄 VIII
第一章 序論 1
第二章 文獻回顧 2
2.1 文獻回顧 2
2.2 電子轉移理論 3
2.3 光致電子轉移分子特性 4
2.4 苯乙烯的光化學反應 7
2.5 苯胺的光化學反應 10
第三章 實驗系統與儀器架設 12
3.1 穩態(steady-state)紫外可見光吸收光譜與螢光分光光譜儀 12
3.2 時間相關單光子計數系統(Time Correlated Single Photon Counting) 12
3.2.1 原理 12
3.2.2 實驗架設 15
3.2 實驗條件 17
3.3 樣品 17
第四章 實驗結果與數據分析 19
4.1 前言 19
4.2 理論計算 20
4.3 實驗結果與數據分析 29
4.3.1 溶劑效應 29
4.3.2 穩態光譜 29
4.3.3 全光譜分析 43
4.3.4 螢光生命期偵測 43
第五章 討論與指認 76
5.1 LE能階放光區生命期之指認 76
5.2 CT state放光區生命期之指認 77
5.3 DA與DAD分子在激發態之動力學比較 79
第六章 結論與未來展望 91
參考文獻 92
附錄 96

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