中文摘要 本論文主要針對本質型螢光感應器與離子錯合所形成的超分子之基態及激發態的光譜行為與特定分子間具有”對等關係 ”的現象作更深入的討論。 本實驗室之前發現化合物4系列在乙腈中與Ca2+金屬離子錯合後的基態及激發態之光譜行為，與以氯作取代的化合物3系列極為相似。為了更進一步了解此”對等關係”的範疇，本論文嘗試將感應分子之接受區monoaza-15-Crown-5作修改，並設計了化合物1系列及2系列。在化合物1系列中，接受區為monoaza-18-Crown-6，當與Ba2+離子錯合時，其光譜行為類似於化合物3系列。化合物2系列的接受區為benzocrown，當其與Ca2+和Mg2+錯合時，其光譜行為仍然類似於化合物3系列。由化合物2-diph與化合物5-diph間之對應關係顯示3，4位置雙氟取代對發光團的影響總和會類似於一個4位置氯取代基。我們利用吸收滴定圖譜，測量化合物1系列及2系列的錯合常數，結果顯示感應分子對離子之錯合能力的強弱，與光譜之”對等關係”無直接的關聯性。 Abstract This thesis was aimed to further study the phenomenon of “ spectral equivalence” between supermolecules and molecules. Our laboratory previously observed a great similarity in both absorbtion and emission spectra between the Ca2+-complexed supermolecules of intrinsic fluorescent probes 4 and the structurally related and Cl-substituted molecules 3 in acetonitrile. To gain a better understanding of the limit and scope of such spectroscopic correlations, We have replaced the monoaza-15-crown-5 ionophore in 4 by monoaza -18-crown-6 and benzo-15-crown-5 to form compound 1 and 2 , respectively. We found that the electronic spectra of complexes 1/Ba2+ resemble those of compound 3 in acetonitrile. Likewise, the spectra of complex 2/Ca2+ and 2/Mg2+ are similar to those of 3 in acetonitrile. On the basis of the electronic spectra of 3-diph and 5-diph, it appears that the overall substituent effect of 3,4-difluoro substitution is similar to that of a 4-chloro substituent. The values of complex stability constant (K) determined by absorbance titration spectra for the metal-ion complexes of probes 1 and 2 have no specific relationship with the above observed spectroscopic correlation.
