含芘基吡唑與苯基三唑取代芳杯之合成及其金屬離子感測研究

Abstract

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.