臺灣博碩士論文加值系統

唑類雜環具有生物活性常被用於配位化學，是非常受歡迎的雜環化合物。近幾年，吡唑雜環化合物非常熱門，其具有的共軛鹼能用於配位化學，已有許多與金屬錯合的文獻報導。本文成功合成出雙芘基吡唑取代的芳杯35與同時修飾上芘基吡唑跟苯基三唑取代之1,3-alternate構形芳杯化合物41。進行紫外-可見光、螢光光譜及氫核磁共振來了解化合物35及41與多種金屬離子間的錯合能力。從紫外-可見光光譜與螢光放射光譜上得知化合物35與41在CHCl3/MeOH (v/v 3/1) 溶劑體系下，沒有加入金屬離子時有明顯的激發雙體放射，而加入Ag+與Hg2+則會有明顯的螢光淬熄，化合物35對Ag+與Hg2+的淬熄分別是95%和97%，化合物41對Ag+與Hg2+的淬熄分別是41%和93%。
另外，藉由Job-plot與氫核磁共振滴定光譜顯示化合物35與41分別以1：1與1：2比例和金屬離子錯合。從螢光光譜上可以得到結合常數分別為3.00 x 104 M-1 (35‧Ag+)、2.99 x 104 M-1 (35‧Hg2+) 和9.24 x 1011 M-1 (41‧2Ag+)、1.46 x 1012 M-1 (41‧2Hg2+)。也從紫外-可見光滴定實驗中，利用Benesi-Hildebrand plot得到化合物35與Ag+離子和Hg2+離子的結合常數，分別為3825 M-1 (35‧Ag+) 和2993 M-1 (35‧Hg2+)。

Azole heterocycles are interesting compounds because many of them are with biological activities and the azole ligands have been widely used in coordination chemistry. Pyrazoles have attracted considerable interest as ligands, because their conjugate bases, pyrazolates, have been found to bind metal ions in a variety of coordination modes. In this thesis, we report the synthesis of a pyrazolyl methylpyrene functionalized calix[4]arene 35 and a 1,3-alternate calix[4]arene 41 with pyrazolyl methylpyrene on the one end and triazolylphenyl on the other end. Metal ion binding abilities of 35 and 41 were invesitigated by UV-vis, fluorescence, and 1H-NMR spectroscopy. Using UV-vis and fluorescence spectra for screening, we found both 35 and 41 show a strong excimer emission as a free ligand, however, they showed a high selectivity toward Ag+ and Hg2+ ions with strong fluorescent quenching in CHCl3/MeOH (v/v = 3/1), respectively. Compound 35 showed 95% quenching of fluorescence by Ag+ and 97% quenching of fluorescence intensity by Hg2+, and compound 41 showed 41% quenching of fluorescence by Ag+ and 93% quenching of fluorescence intensity by Hg2+.
Furthermore, the Job Plot and 1H-NMR titration experiment showed that the binding ratio of 35 toward Ag+ and Hg2+ were both 1:1 complex, and 41 toward Ag+ and Hg2+ were both 1:2 complex. The binding constant of 35 with Ag+ and Hg2+ was determined by fluorescence quenching to be 3.00 × 104 M-1 and 2.99 × 104 M-1, respectively. While the binding constant of 41 with Ag+ and Hg2+ was determined similarly to be 9.24 × 1011 M-1 and 1.46 × 1012 M-1, respectively. The binding constants of 35 with Ag+ and Hg2+ were also determined using UV-vis method to be 3825 and 2993 M-1, respectively.

中文摘要 I
Abstract III
目錄 V
圖目錄 IX
式圖目錄 XVIII
化合物對照表 XX
第一章 緒論 1
1.1 超分子化學 1
1.2 芳杯 (calix[n]arene) 2
1.2.1 芳杯之合成與構形 3
1.2.2 芳杯衍生化反應 5
1.3 化學感測器的設計原理 6
1.4 化學感測分子 7
1.4.1 螢光化學感測分子 (Fluorescent Chemosensor) 7
1.4.2 螢光感測分子之訊號傳遞機制 9
1.4.2.1 光誘導電子轉移 (photoinduced electron transfer，PET)28, 10
1.4.2.2 光誘導電荷轉移 (photoinduced charge tranfer，PCT)29 11
1.4.2.3 單體-激態雙體之形成 (Formation of Monomer-Excimer)29, 12
1.4.3 芘 (pyrene) 在螢光感測器上的特性與應用 15
1.4.4 雙位接收器 (ditopic receptor) 之研究 18
1.5 吡唑化合物之簡介 24
1.5.1 吡唑之製備方式 25
1.5.2 吡唑化合物之性質探討 26
1.5.3 吡唑化合物於感測器上之應用例子 27
1.5.3.1 六吡唑對於NH4PF6 之辨識 27
1.5.3.2 吡唑芳杯對金屬之辨識43 29
1.6 即合化學(Click Chemistry) 30
1.6.1 三唑介紹 31
1.6.2 含三唑之1,3-alternate構形芳杯實例 32
第二章 研究動機 34
第三章 結果與討論 36
3.1 25, 26, 27, 28 – Tetrahydroxycalix[4]arene之合成研究 36
3.1.1 p-tert-Butylcalix[4]arene 之合成 36
3.1.2 25, 26, 27, 28 – Tetrahydroxycalix[4]arene 27之合成 37
3.2 化合物31之合成步驟 38
3.2.1 化合物29之合成 39
3.2.2 化合物31之合成 40
3.3 吡唑化合物32之合成 41
3.4 含溴之吡唑化合物33之合成步驟 42
3.5 下緣芘基吡唑取代芳杯化合物35之合成步驟 43
3.5.1 合成含芘基吡唑之控制化合物36 44
3.6 雙炔取代之芳杯38之合成 45
3.7 含下緣吡唑與上緣三唑取代1,3-交錯構形芳杯41之合成 45
3.7.2 合成化合物40 47
3.7.3 合成化合物41 48
3.8 化合物的NMR光譜與結構鑑定 48
3.8.1 芳杯化合物35的氫譜訊號標定 49
3.8.2 芳杯化合物41的氫譜訊號標定 57
3.9 芳杯35、41與36氯仿/甲醇 (v/v = 3:1) 溶液下之金屬螯合能力研究 63
3.9.1 芳杯化合物35的金屬離子初步篩選能力之研究 65
3.9.2 含芘基吡唑控制化合物36對金屬離子的篩選能力研究 68
3.9.3 1,3-Alternate構形芳杯化合物41的金屬離子初步篩選能力之研究 70
3.9.4 芳杯35對Ag+的紫外-可見光與螢光光譜詳細滴定實驗 72
3.9.5 芳杯35對Hg2+的紫外-可見光與螢光光譜詳細滴定實驗 76
3.9.6 芳杯化合物41對Ag+的紫外-可見光與螢光光譜詳細滴定實驗 79
3.9.7 芳杯化合物41對Hg2+的紫外-可見光與螢光光譜詳細滴定實驗 81
3.10 化合物35和41之核磁共振光譜詳細滴定研究 83
3.10.1 化合物35於氘氯仿/氘甲醇 (v/v = 3:1) 中對Ag+離子之氫核磁共振光譜詳細滴定研究 84
3.10.2 化合物35於氘氯仿/氘甲醇 (v/v = 3:1) 中對Hg2+離子之氫核磁共振光譜詳細滴定研究 88
3.10.3 化合物41於氘氯仿/氘甲醇 (v/v = 3:1) 中對Ag+離子之氫核磁共振光譜詳細滴定研究 92
3.10.4 化合物41於氘氯仿/氘甲醇 (v/v = 3:1) 中對Hg2+離子之氫核磁共振光譜詳細滴定研究 96
3.11 化合物35與41對Ag+離子與Hg2+離子之現象討論 98
第四章 結論 99
第五章 實驗部分 101
第六章 參考文獻 114
附圖 ………………………………………………………………….......116
簡歷 ………………………………………………………………….......142

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