臺灣博碩士論文加值系統

在本論文中，我們合成了兩種具有偵測重金屬能力的銥(III)金屬錯合物：[Ir(pba)2(pbi)]以及[Ir(pba)2(pbi)]。位在配位基pbi上之氮原子所具有的孤電子對讓我們得以具有偵測Hg2+、Ce3+、Cr3+以及Fe3+等金屬離子的能力。氮原子與這些金屬陽離子之間的作用力表現在吸收光譜與放光光譜的變化中。從吸收光譜中我們可以看到等吸收點的存在，而從放光光譜中我們也發現了與金屬離子結合前後，錯合物的放光強度也有不同程度的改變。我們使用了B3LYP的理論方法，並配合基底函數6-31G*後，得以從密度泛函理論中找到解釋這些光物理現象變化的方法。此論文也是本實驗室第一篇藉由理論計算結果而成功預測吸收光譜位移現象的論文。 為了確認錯合物中醛基以及氫氧基的部位確實沒有與金屬陽離子結合的能力，我們也合成出[Ir(pba)2(bpy)][Cl]以及[Ir(ppm)2(bpy)][Cl]以作為對照。即使[Ir(pba)2(bpy)][Cl]的放光強度比[Ir(pba)2(pbi)]還要強很多，但是[Ir(pba)2(bpy)][Cl]依然沒有表現出能夠偵測任何金屬的能力。值得注意的是，[Ir(ppm)2(bpy)][Cl]這個經過還原後的衍生物表現出可以稍微偵測到Ag+、Ca2+、Ni2+以及Zn2+的能力。同時我們也發現到此錯合物對於水有著極佳的溶解度。

Two Ir(III)-complexes, [Ir(pba)2(pbi)] and [Ir(ppm)2(pbi)] {pba = 4-(pyridin-2-yl)benzaldehyde,pbi=2-(pyridin-2-yl)-1H-benzo[d]imidazole , ppm=(4-(pyridin-2-yl)phenyl)methanol }, capable of sensing heavy metal ions have been synthesized in this study. The lone-paired electrons on the nitrogen atom of the pbi ligand is responsible for detecting the following metal ions: Hg2+, Ce3+,Cr3+ and Fe3+. The N(pbi)—metal Ion interactions result in variations of both UV-Vis spectra (by a blue-shift of about 7 nm) and luminescence spectra (by the change of luminescence intensities). These changes of photophysical data have found to be well predicted by the density functional theory calculations using B3LYP correlation-exchange functional formalism and 6-31G* basis set. More interestingly, the calculated results have been FIRST employed at this lab to successfully predict the directions of the shift (red or blue) in a UV-Vis absorbance-wavelength profile. In order to examine the failure of the carbonyl (in pba) or the hydroxyl oxygen atoms in semi-coordination with metal ions, we have also prepared [Ir(pba)2(bpy)][Cl], in which the carbonyl oxygen loses the ability to detect metal ions at all although the luminescence intensities were much higher than [Ir(pba)2(pbi)]. It is noteworthy that the reduced analogue,[ Ir(ppm)2(bpy)][Cl], has revealed a slight ability to detect some metal ions including Ag+, Ca2+, Ni2+ and Zn2+. Nonetheless, this poor sensor nature of [Ir(ppm) 2(bpy)][Cl] could be, more or less, counterbalanced by its high solubility in water.

摘要.......................................................................I
Abstract..................................................................II
謝誌.....................................................................III
目錄.......................................................................V
表目錄..................................................................VIII
圖目錄....................................................................IX
第一章 緒論...............................................................1
1-1 Type1-冠狀醚型感測器(crown ether) ...............................1
1-2 Type2-枝鏈型感測器(side chain) ..................................4
1-3 Type3-探頭型感測器(probe) .......................................5
1-4 常用的結構與簡稱.................................................8
第二章 實驗部分與錯合物色譜變化...........................................9
2-1 錯合物簡介.......................................................9
2-2 合成實驗部分....................................................11
2-2-1 儀器設備........................................................11
2-2-2 藥品............................................................12
2-2-3 實驗部分........................................................13
2-3 分析實驗部分....................................................16
2-3-1 儀器設備........................................................16
2-3-2 藥品............................................................19
2-3-3 實驗操作........................................................19
2-4 由吸收光譜與放光光譜判斷感測器的離子選擇性......................21
2-4-1 錯合物3-[Ir(pba)2(bpy)](Cl) ....................................21
2-4-2 錯合物2-[Ir(pba)2(pbi)] ........................................22
2-4-3 錯合物5-[Ir(ppm)2(bpy)](Cl) ....................................24
2-4-4 錯合物4-[Ir(ppm)2(pbi)] ........................................25
2-4-5 分析實驗之結果與討論............................................26
2-5 錯合物色譜變化的討論............................................27
2-5-1 官能基修飾與色譜變化的關係......................................28
2-5-2 金屬結合前後之色譜變化..........................................30
2-5-3 錯合物色譜變化的結果與討論......................................32
第三章 計算原理與方法..................................................................... ..34
3-1 計算原理....................................................................................34
3-1-1 Density Functional Theory 理論方法.........................34
3-1-2 基底....................................................................................36
3-1-3 分裂 (split) 基底..........................................................37
3-1-4 天然鍵結軌域 (NBO) .......................................................38
3-2 吸收光譜概論………………………………………………..40
3-3 進階TD-DFT理論計算結果分析方法.....................................43
3-4 結果與討論…………………………………………………..57
第四章 參考文獻……………………………………………………..59
第五章 附錄…………………………………………………………..62

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