吡唑芳杯作為螢光金屬離子感測器及柱形杯芳烴衍生物之合成

Abstract

本研究主要分為二部分，第一部份乃利用芳杯分子為骨架，成功地在芳杯下緣修飾兩系列之吡唑官能基，其中以含有苯基之吡唑芳杯為合成基本架構，隨後並以含有苯基蒽之吡唑芳杯76與77為主要篩選金屬離子之主體分子。我們同時合成了以丙基將剩餘羥基保護起來的控制化合物78與79，並進行紫外–可見光光譜、螢光放射光譜與氫核磁共振光譜的量測，以觀察吡唑芳杯76–79與16種金屬離子的辨識能力，發現在甲醇/氯仿 (v/v = 4:1) 溶劑體系下，吡唑芳杯77與79分別對Ag+與Hg2+有專一選擇性，且吡唑芳杯77對於Ag+具有螢光增強141%之效應，而吡唑芳杯79則對Hg2+有螢光淬熄51%之現象。另外，由Job plot與氫核磁共振滴定光譜的結果顯示，吡唑芳杯77與79分別對Ag+與Hg2+分別傾向於以1:1之化學計量比進行錯合在下緣吡唑官能基上，且由Hill plot與Stern-Volmer plot找出其錯合常數，分別為(1.12 ± 0.17) × 104 M-1、(1.33 ± 0.20) × 104 M-1。第二部分則是研究柱形杯芳烴之合成條件，藉由三氟化硼的催化下，將含有雙取代基之單體與多聚甲醛在濃度為0.1 M之條件下進行合環反應，成功且快速地合成出高產率之柱形杯芳烴38與83；另外，我們將兩種不同單體以4:1之混合比例，利用上述條件，成功地在柱形杯芳烴上選擇性地引入雙丙炔基95。

This study is divided into two parts. First, two series of lower-rim modified calix[4]arene with pyrazole substituents were synthesized. Using phenyl pyrazole calix[4]arenes as basic synthesis frameworks, we synthesized phenylanthryl pyrazole calix[4]arenes 76 and 77 and control compounds 78 and 79 as fluorogenic ions sensors. Based on the results from UV-Vis, fluorescence and 1H-NMR spectrometry, we found that pyrazole calix[4]arenes 77 and 79 recognized Ag+ and Hg2+ with excellent selectivity in MeOH/CHCl3 (v/v = 4:1), respectively. Compound 77 induced 141% enhancement of fluorescence intensity toward Ag+, and compound 79 showed 51% fluorescence quenching effect toward Hg2+.Furthermore, the complexation of compound 77 with Ag+ and 79 with Hg2+ both showed 1:1 host-guest stoichiometry based on by Job plot obtained from fluorescence and 1H-NMR titration spectra. We also found the binding constants of 77 with Ag+ was (1.12 ± 0.17) × 104 M-1 and 79 with Hg2+ was (1.33 ± 0.20) × 104 M-1.Second, the research was focused on the reaction condition to synthesize pillar[5]arenes. Pillar[5]arenes 38 and 83 were successfully and facile synthesized by cyclization reaction with high yield. These compounds were obtained via borontrifloride etherate catalyzed procedure with 1,4-dialkoxyphenyl monomer and paraformaldehyde under 0.1 M solution. Besides, a synthetic route to difunctional pillar[5]arene 95 was also developed by combining two different monomers with 4:1 ratio using the conditions stated above.