| 摘要: | 中文摘要 本論文根據ICT原理設計並合成出數種本質型螢光離子感應器1-Py、1-Ph、1-PM和1-FM，結構以皇冠醚monoaza-15-crown-5 (A15C5) 為接受器，而發光團以二苯乙烯為主體。為了比較，我們亦探討已知化合物1-Me。 在乙腈中，系列一化合物 (1-Py、1-Ph、1-PM、1-FM和1-Me)對Ca2+離子錯合後有螢光位移現象，其中化合物1-Py之螢光光譜呈藍位移，而化合物1-FM則無明顯位移，其餘三個感應分子皆為紅位移；至於此五個感應分子之吸收光譜改變則較單純，皆為藍位移。儘管如此，此五個感應分子與Ca2+離子錯合後的光譜行為，包括放射與吸收光譜、螢光量子產率和螢光生命期皆與化合物系列三 (3-Py、3-Ph、3-PM、3-FM和3-Me) 相似；而在二氯甲烷中，化合物系列一與Na+離子錯合後，其光譜行為亦相似於化合物系列三。此結果顯示 A15C5/Ca2+在乙腈中和A15C5/Na+在二氯甲烷中的電子效應相當於一個氯取代基。既然放射與吸收螢光皆與氯取代之化合物系列三相似，顯示感應錯合物在激發態時，金屬離子仍存在於接受器之內；此對等關係除對新型螢光感應器的設計有幫助外，亦可藉由對氯取代之化合物之探討研究，能讓我們對此類超分子之電子結構與感應機制有更深入了解。 Abstract In this thesis, we report the design and synthesis of four new ICT-based intrinsic fluoroionophores 1-Py, 1-Ph, 1-PM, and 1-FM, which use monoaza-15-crown-5 (A15C5) as the ionophore and aminostilbene as the fluorophore. For comparison, we also investigated the known compound 1-Me. Except for 1-FM, compound series number one (1-Py, 1-Ph, 1-PM, 1-FM, and 1-Me) display fluorescence shifts in response to Ca2+ in acetonitrile. The fluorescence of compound 1-Py is blue-shifted, whereas it is red-shifted for the other three compounds. On the other hand, all five compounds display blue shift in their absorption spectra. Although the spectral responses are distinct, the resulting complexes display a spectroscopic behavior, including the absorption and emission shape and energy, fluorescence quantum yield, and fluorescence lifetime, similar to the corresponding compound series number three (3-Py, 3-Ph, 3-PM, 3-FM, and 3-Me). In dichloromethane, the complexation between compound series number one and Na+ also results in a photochemical behavior similar to the compound series number three. Such correlations indicate that A15C5/Ca2+ in acetonitrile and A15C5/Na+ in dichloromethane have an electronic effect nearly equivalent to a chloro substituent. Since the similarities exist in both absorption and emission spectra in all five fluoroionophores, this suggests that the excited-state decoordination reaction does not occur in all cases. The observed correlations might serve as a useful guide for future probe design. Furthermore, we can gain insights into the electronic structures of the complexes (supramolecular entities) based on the studies of their correlated molecules. |
