邱勝賢臺灣大學：化學研究所江品璁Chiang, Pinn-TsongPinn-TsongChiang2007-11-262018-07-102007-11-262018-07-102005http://ntur.lib.ntu.edu.tw//handle/246246/51661我們在此論文當中成功的合成出一具有TTF之分子夾1a。我們以文獻上已知之glycoluril為基礎之分子夾2為基礎，與2-thioxo-1,3-dithiole在酸催化下進行縮合反應得到分子夾3。利用triethylene glycol monomethyl ether tosylate在鹼性條件之下修飾分子夾3上之酚基，得到分子夾5a，以Hg(OAc)2進行一個硫氧置換反應得到分子夾6a，以此分子夾與1,3-dithiole-2-thione進行一個HWE反應得到分子夾1a。 我們發現具TTF側臂之分子夾與缺乏電子之大環分子之間可形成大環–分子夾之錯合體。運用鉀離子–穴醚、酸–鹼、氧化–還原、冷卻–加熱等外加刺激，可控制此一大環–分子夾錯合體循環於解離與錯合的二種不同狀態。 由於此二種狀態各自呈現不同顏色，此一大環–分子夾錯合體不但可作為一個四向控制之分子開關，還能模擬一個三輸入NOR邏輯閘的表現。Herein, we synthesized a TTF contained molecular clip 1a. Under acidic condition, the known molecular clip 2 underwent a condensation reaction with 2-thioxo-1,3-dithiole. The resulting product 3 was then modified on the phenolic groups with triethylene glycol monomethyl ether tosylate to get molecular clip 5a. 5a was treated with Hg(OAc)2 to convert thione into ketone (6a). Then the resulting molecular clip 6a was reacted with 1,3-dithiole-2-thione in presence of P(OEt)3 to afford 1a. We found such TTF contained molecular clip that forms a macrocycle – molecular clip complex with a electronic complementary macrocycle. Four different sets of external stimuli – the K+/[2,2,2]cryptand, NH4+/Et3N, (p-PhBr)3NSbCl6/Zn pairs and heating/cooling cycles – allow the movement of this molecular switch to be controlled between its threaded and unthreaded states. The macrocycle – molecular clip complex not only considered as a quadruply controllable molecular switch but also can be operated by three of these stimuli as a three-input molecular NOR-functioning logic gate that may be monitored by UV-Vis spectroscopy.摘要 ················································· I 論文發表 ············································· III 目錄 ················································· IV 圖表 ················································· VI 表格 ················································· IX 壹、緒 論 ············································ 1 1.1 前言 ·········································· 1 1.2 人造超分子系統 ································ 3 1.2.1 早期的人造分子機械 ······················· 3 1.2.2 利用酸鹼控制的分子開關 ··················· 3 1.2.3 以可逆氧化還原反應控制之分子開關 ········· 5 1.2.4 以光化學控制的分子開關 ··················· 7 1.2.5 分子構型對於鍵結的影響 ··················· 8 1.3 多向控制分子開關的設計方向與問題 ·············· 10 貳、結 果 與 討 論 ··································· 12 2.1 研究動機與研究方向 ···························· 12 2.1.1 研究動機 ································· 12 2.1.2 大環–分子夾錯合體之設計及預期之功能 ······ 12 V 2.2 含TTF分子夾之合成 ··························· 15 2.3 分子夾上TTF之重要性研究 ····················· 18 2.4 構築大環–分子夾錯合體 ························ 21 2.4.1大環分子9·2PF6與分子夾1a生成之大環–分子夾 錯合體 ····································21 2.4.2 分子夾1a-c的性質探討 ····················· 24 2.4.3 構築可控制版本之大環–分子夾錯合體 ······· 26 2.5 以大環–分子夾錯合體構築之分子開關功能研究 ···· 28 2.5.1 以大環分子接受外加刺激的分子開關控制方法 · 28 2.5.2 利用溫度改變超分子錯狀態之分子開關控制方法 32 2.5.3 利用氧化還原分子夾上TTF部份之分子開關控制 方法 ····································· 33 2.6 大環–分子夾錯合體建構之四向控制分子開關及其功能 35 參、結 論 ··········································· 37 肆、實 驗 部 份 ····································· 38 伍、參 考 文 獻 ····································· 52 附 錄：Job plot與結合常數測量、1H與13C核磁共振光譜6564095 bytesapplication/pdfen-US超分子化學大環-分子夾錯合體分子開關supramolecular chemistrymacrocycle - molecular clip complexmolecular switchthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/51661/1/ntu-94-R92223044-1.pdf