指導教授：楊吉水臺灣大學：化學研究所莊博雅Chuang, Po-YaPo-YaChuang2014-11-252018-07-102014-11-252018-07-102014http://ntur.lib.ntu.edu.tw//handle/246246/261352五苯荑分子有三維空間性質、結構剛硬且對稱，可預期此結構作為分子機械 的潛力，本實驗室長期研究五苯荑分子合成與官能基化，並將其引入設計分子煞 車。本篇論文主要為合成與探討新型分子的煞車系統，以五苯荑分子作為轉子， 一端引入可進行光、熱異構化的偶氮雙鍵，並連接雙取代的苯環作為分子煞車器， 以期利用光、熱操控分子應用於分子機械元件的設計，設計出分子2OR。此外， 五苯荑分子的另一端引入不同取代基針對分子的光轉換效率與熱異構化行為之 改良，設計分子2R，並加入2NR 進行討論。 我們利用變溫2D-EXSY 探討轉子於煞車態之轉動速率、與轉動之動力學參 數，當化合物系列2 之分子在順式結構時 (c-2)，轉子與煞車器之間由於立體障 礙造成連接轉子之單鍵快速旋轉受阻礙，而旋轉速度減慢，煞車啟動 (brake on)； 反式結構時 (t-2)，無明顯立體障礙，連接轉子的單鍵可快速旋轉，煞車關閉 (brake off)，兩狀態轉速差異可達109 倍。以光化學控制偶氮苯的異構化，可將反 式轉換為大部分順式之光穩定態，三者轉換效率皆可達75%，其中2OR 與2R 有較好的表現; 以紫外光254 nm 可將部分順式轉換回反式至光穩定態，三者轉 換效率皆可達80%，總轉換效率可達55%以上。另外，藉偶氮苯之熱異構化特 性，長時間操作可將順式完全轉換為反式，其中，2NR 為較強之推拉電子組合， 熱異構化速率較快。結合光熱控制可使此系列 (2) 之分子煞車總轉換效率達 75%。相較以二苯乙烯為光異構化切換之1OR，效率有375 %的提升。We have adopted the rigid H-shaped pentiptycene scaffold as a four-bladed rotor to create new light-controlled molecular brakes. In this thesis, a series of new pentiptycene-derived molecular brakes 2OR, 2R and 2NR containing the well-known photochromic azobenzene group were delveloped, and the substituent effect on the photochemical and thermal isomerization was investagated. The rotational rates and kinetic parameters of c-2 were probed by 2D-EXSY. The results showed that the rotational rate of the brake-on state (c-2) is lower by ~109 fold than the brake-off state (t-2). Furthermore, the brake can be switched off in two different ways, i.e., photochemical and thermal switching. The overall photoreversibility between t-2 and c-2 in hexane was as high as 55%. Further improvement on switching efficiency can be achieved with themo reset from c-2 to t-2 is achievable, which lead to a total efficiency of 75%. Compared to the previous stilbene system, the total switching efficiency is enhanced by almost 375%.謝誌................................................................................................................................ i 中文摘要........................................................................................................................ ii Abstract ........................................................................................................................ iii 目錄............................................................................................................................... iv 圖目錄.......................................................................................................................... vii 表目錄........................................................................................................................ xiii 附圖目錄.................................................................................................................... xiii 第一章 前言.................................................................................................................. 1 1-1 機械簡介1 ...................................................................................................... 1 1-2 人造分子機械 ................................................................................................ 3 1-2-1 人造分子機械之要素1a, 9 ................................................................... 3 1-2-2 化學能驅動之分子機械 ..................................................................... 4 1-2-3 光能驅動之分子機械 ......................................................................... 6 1-2-4 電能驅動之分子機械 ......................................................................... 9 1-2-5 熱能驅動之分子機械 ....................................................................... 10 1-3 異構化作用 ................................................................................................... 15 1-3-1 二苯乙烯光異構化24 ....................................................................... 17 1-3-2 偶氮苯光異構化26 ........................................................................... 19 1-3-3 偶氮苯熱異構化 ............................................................................... 22 1-4 動態NMR (Dynamic NMR) 32 .................................................................... 27 1-4-1 譜線形狀分析 (Line-shape analysis, LSA)32 .................................. 28 1-4-2 交換光譜 (2D-exchange spectrum, 2D-EXSY)32 ............................ 29 1-5 苯荑 (iptycene)分子介紹 ............................................................................ 33 1-5-1 苯荑分子的結構與命名 ................................................................... 33 1-5-2 五苯荑分子 ....................................................................................... 34 1-5-3 五苯荑分子之官能基化 ................................................................... 34 1-5-4 五苯荑分子之分子機械 ................................................................... 37 1-6 研究動機 ...................................................................................................... 41 第二章 結果與討論.................................................................................................... 43 2-1 化合物之合成 .............................................................................................. 43 2-1-1 目標化合物逆合成分析 ................................................................... 43 2-1-2 目標化合物之合成 ........................................................................... 43 2-2 化合物之結構與性質 .................................................................................. 46 2-2-1 化合物2OR 的結構與NMR 圖譜 ................................................... 46 2-2-2 化合物2R 與2NR 的結構與NMR 圖譜......................................... 53 2-2-3 反式化合物的X-ray 單晶繞射結構 ................................................ 65 2-2-4 順式化合物的2D-EXSY 光譜性質 ................................................ 67 2-3 化合物的光學性質 ...................................................................................... 80 2-3-1 反式化合物之吸收光譜 .................................................................... 80 2-3-2 化合物之光異構化性質 .................................................................... 82 2-3-3 順式化合物之吸收光譜 ................................................................... 86 2-3-4 化合物之光轉換效率 ........................................................................ 90 2-4 順式化合物的熱異構化行為 ...................................................................... 92 2-5 化合物的整體轉換 ...................................................................................... 98 2-5-1 以光控化合物轉換 ............................................................................ 98 2-5-1 以光熱雙控化合物轉換 .................................................................. 100 第三章 結論.............................................................................................................. 103 第四章 實驗部分...................................................................................................... 104 4-1 實驗藥品與溶劑 ........................................................................................ 104 4-2 實驗儀器 .................................................................................................... 108 4-3 實驗步驟 .................................................................................................... 110 參考資料.................................................................................................................... 120 附圖............................................................................................................................ 12518287019 bytesapplication/pdf論文使用權限：不同意授權五苯荑偶氮苯分子機械thesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/261352/1/ntu-103-R01223174-1.pdf