(I) 三亞苯三唑橋聯雙柱芳烴之合成及其對吡啶與咪唑陽離子辨識研究 (II) 芘基吡唑取代芳杯對銀離子與汞離子之感測研究

Abstract

本論文透過點擊反應成功合成出三亞苯三唑橋聯雙柱芳烴37、三亞苯三唑單取代柱芳烴41以及二苯乙烯三唑橋聯雙柱芳烴47。由螢光初步篩選結果決定以化合物37作為主體，對吡啶與咪唑陽離子客體G3-G5探討，化合物41則針對G5作討論，化合物47因二苯乙烯光照順反異構化之特性導致螢光性質消失，無法利用螢光光譜做探討。透過紫外-可見光光譜與螢光光譜，以及Hill equation計算，再加上氫核磁共振滴定實驗結果，可以確定主客體結合常數 3•G3 > 37•G5 > 37•G4，分別為2.21 × 105 M-2、5.83 × 104 M-2與2.12 × 104 M-1，而主客體錯合比例則由高解析質譜 (電灑游離法) 確認分別為1:2、1:2與1:1錯合；錯合物41•G5利用同樣方法求得結合常數為4.37 × 103 M-1，主客體以1:1錯合。 若是改變咪唑陽離子G5之配位陰離子，分別為客體G6-G8，並與化合物37錯合，可發現當陰離子的配位強度越弱，其陽離子對主體會有越強的螢光增強效果，以客體G8最佳，在加入100當量時，增強效果達到60.1%，遠高於G5-G7；若是改變咪唑陽離子G8之碳鏈長度，分別為客體G9-G11，則沒有明顯觀察到碳鏈長度對錯合強弱的影響。輔以氫核磁共振滴定實驗之結果，我們推測客體皆傾向由主體柱芳烴沒有橋聯基的一端，以陽離子端進入柱芳烴孔洞中，客體碳鏈裸露在孔洞外。 本論文的另一部分則是接續實驗室陳胤儒學長的研究。在學長的研究中，成功合成出雙芘基吡唑取代芳杯28與同時具有芘基吡唑與苯基三唑的1,3-交錯構形芳杯29，兩者皆對Ag+與Hg2+有良好的篩選能力，但芳杯28無法確定與金屬離子的錯合比例，芳杯29則缺少能與其對照之控制化合物58，因此本研究重新製備芳杯28並成功合成控制化合物58，且透過Job plot以及高解析質譜，確定芳杯28 與Ag+、Hg2+離子皆為1:1錯合。 由初步篩選的結果，發現化合物58對Ag+、Hg2+離子亦有良好的篩選能力，透過螢光光譜與Hill equation求得其結合常數分別為3.89 × 107 M-4 與3.06 × 107 M-4，與芳杯28、29對比，結合常數的大小29•Ag+ > 58•Ag+ > 28•Ag+以及29•Hg2+ > 58•Hg2+ > 28•Ag2+，顯示控制化合物的上緣丙醚基也能協助螯合金屬離子，雖效果不如三唑基團，但此結合常數遠高於只螯合一個金屬離子的芳杯28，綜合Hill plot、Job plot與氫核磁共振滴定實驗之結果，推測芳杯58與金屬離子以2:3錯合。

In this study, we have synthesized triphenylenyl triazole bridged pillar[5]arene dimer, triphenylenyl triazole substituted pillar[5]arene and stilbene triazole bridged pillar[5]arene dimer as compound 37, 41, 47, respectively. Based on the results from UV-Vis absorption spectroscopy and fluorescence emission spectroscopy, compound 37 showed good binding abilities toward pyridinium cations G3-G4 and imidazolium cation G5, and compound 41 showed good binding abilities toward G5 only. But, we won’t study compound 47 furthmore, which fluorescence characteristic vanished after exposured by UV light, because of trans-cis isomerism of stilbene group. According to the more detail research of UV-Vis spectroscopy, fluorescence spectroscopy, Hill plot and 1H NMR titration, we found that binding ability 37•G3 > 37•G5 > 37•G4, which binding constant were 2.21 × 105 M-2, 5.83 × 104 M-2 and 2.12 × 104 M-1, determing by Hill equation. Furthermore, the high resoluition mass spectrometry showed that the binding ratio of 37 toward G3, G5 and G4 were 1:2, 1:2 and 1:1, respectively. The same method were used to confirm that binding constant and binding ratio of compound 41 toward G5 were 4.37 × 103 M-1 and 1:1. Compound 37 showed binding abilities toward imidazolium cations guest G6-G8, which have different anion Cl-, BF4- and PF6-. Fluorescence intensity of host 37 have best fluorescence enhancement effect when G8 was added, compared with G5-G7. However, there is no significant difference of binding constant between guest G8-G11, which alkyl group have different carbon chain length, toward compound 37. Based on the discussion of binding ability of compound 37 toward G8-G11 and 1H NMR titration, we surmised that guest compounds using cation side to penetrate into the cavity of pillar[5]arene from the side without substituted or bridged group and alkyl chain of guest are outside host cavity. The other part of the study is according to the previous work of laboratory upperclassmen, Yin-Ju Chen. In his study, he reported the synthesis of a pyrazolyl methylpyrene functionalized calix[4]arene 28 and 1,3-alternate calix[4]arene 29 with pyrazolyl methylpyrene on the one end and triazolylphenyl on the other end. These two compound showed good binding ability toward Ag+ and Hg2+, but the binding ratio of compound 28 toward metal ion was ambiguous and compound 29 lack the control compound 58 to comparison. Therefore, we prepared compound 28 and confirmed the binding ratio were 1:1 toward Ag+ and Hg2+ by Job plot and high resoluition mass spectrometry. Besides, we successfully synthesized control compound 58. Based on the results from UV-Vis spectroscopy and fluorescence spectroscopy, same as compound 28, 29, compound 58 showed good binding abilities toward Ag+ and Hg2+, and binding constant were calculated for 3.89 × 107 M-4 and 3.06 × 107 M-4 by Hill equation. Compared with compound 28, 29, binding constant 29·Ag+ > 58·Ag+ > 28·Ag+ and 29·Hg2+ > 58·Hg2+ > 28·Ag2+. This result indicated the propyl group at the upper-rim of control compound 58 would assist to bind metal ion, although it’s not effective as triazole group. According to the binding constant order, Hill plot, Job plot and 1H NMR titration, we surmised that compound 58 have binding ratio 2:3 toward Ag+ and Hg2+.