臺灣博碩士論文加值系統

單一功能材料的發展已非常普遍，而多功能化刺激響應性材料豐富的應用前景將成為未來發展的趨勢，但設計並控制複雜的分子排列仍是一項極其困難的工作。本文成功利用兩次點擊化學反應合成之含芳杯冠醚大環、三唑鎓基團及氟硼二吡咯多官能基之啞鈴型化合物T1、T2與[2]輪烷分子R1、R2。我們發現化合物T2及R2對H2PO4−離子具高選擇性，且透過Job’s plot計算出T2與R2和H2PO4–離子以1:1 (或者2:2)比例錯合，其中T2的錯合常數為3700 M1。為研究BODIPY聚集的螢光性質，我們將化合物溶解於乙腈與水的混和溶劑中，當水的比例分別達到90%、70%和80%時，化合物T1、R1與R2會因分子間的π-π堆疊表現出螢光淬熄。
透過核磁共振光譜與2D-ROESY及高解析質譜等技術可明確提供[2]輪烷生成之證據，雖然引入芳杯冠醚大環的[2]輪烷R2-b無法如預期從管柱中純化得到，但此複雜系統仍可透過酸鹼的調控，驅動芳杯冠醚大環在二級銨鹽與三唑鎓基團兩個車站之間往返。

The evolution of materials changes with each passing day, and rich application prospects of multi-functional stimuli-responsive materials would be the future trends. However, it is still extremely difficult to design and control the packing arrangement of these complex molecules. In this thesis, dumbbell-shaped molecules (T1 and T2) and [2]rotaxanes (R1 and R2) containing t-butylcalix[4]arene macrocycle, triazolium groups, and BODIPY groups were designed and synthesized with multiple components by double click reaction. We found compounds, T2 and R2 could show high selectivity to H2PO4− ions and the complexation ratio was determined by Job’s plot to be 1:1 (or 2:2) for both compounds and the Ka of T2 is 3700 M-1. Further studies of fluorescent properties of BODIPY in its aggregation state were carried out by dissolving these compounds in co-solvent of acetonitrile and water. When water fraction was increased to 90%, 70%, and 80% the fluorescence of compounds T1, R1, and R2 were quenched which could be due to intermolecular π-π stacking interactions.
1H NMR, 2D-ROESY and high-resolution mass spectrometry were used to confirm the formation of [2]rotaxanes R1 and R2. Although [2]rotaxane R2-b could not be purified by column chromtagrophy as we hope, the reversible shuttling motion of the t-butylcalix[4]calixarene macrocycle along the axle between two stations (R2NH2+ and triazolium groups) can be driven by adding acid and base.

中文摘要 i
Abstract iv
目錄 vii
圖目錄 ix
式圖目錄 xiii
附圖目錄 xiv
目標分子結構對照表 xvii

第一章 緒論 1
1.1 超分子化學簡介 1
1.2 機械互鎖分子 2
1.3 輪烷分子合成 4
1.4 點擊化學 5
1.4.1 銅催化疊氮炔環加成反應 6
1.5 分子梭 (molecular shuttle) 7
1.6 氟硼二吡咯(BODIPY)螢光團的特性及應用 11
1.6.1 BODIPY應用於輪烷之相關文獻 13
1.7 聚集誘導發光性質 17
1.7.1 聚集誘導發光應用於輪烷之相關文獻 18

第二章 研究動機 21

第三章 結果與討論 23
3.1 含氟硼二吡咯輪烷之合成策略 23
3.1.1 目標分子R4與對照分子R2之逆合成分析 23
3.1.2 合成路徑探討 27
3.2 化合物T1、T2、R1、R2及R2-b之1H NMR光譜與結構鑑定 40
3.2.1啞鈴型分子T1與T2之氫譜訊號標定 40
3.2.2 [2]輪烷R1與R2之氫譜訊號標定 45
3.3 螢光性質探討 61
3.3.1 化合物T1、T2、R1與R2對H2PO4–離子之選擇性 62
3.3.2 化合物T1、T2、R1與R2之BODIPY Aggregation測試 72
3.4 化合物T2與R2對H2PO4–離子錯合比例之測定 81

第四章 結論 90

第五章 實驗步驟 92
5.1試藥及測試方法 92
5.2實驗合成步驟及光譜資料 93

第六章 參考文獻 111

附圖 117

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