含3-(2'-吡啶基)-1,2,4-三氮唑衍生物之錸金屬錯合物：合成、光物理性質及其陰離子感測研究

Abstract

本論文主要探討兩個含有 3-(2'-吡啶基)-1,2,4-三氮唑配位子之錸金屬錯合物之陰離子感測行為，並且經由核磁共振光譜、高解析質譜分析及單晶結構繞射進行純度及結構鑑定，發現由於三氮唑配位子能以不同位置的氮原子進行配位反應，因此所得之錯合物 DL25-A 與 DL25-B 為結構異構物。並且在乙腈溶劑中，經由紫外光-可見光吸收、放光及核磁共振等滴定實驗，對其進行陰離子感應測試；由測試結果得知，當陰離子加入時其吸收及放光光譜皆會呈現藍位移的變化趨勢，並且由核磁共振光譜證實，兩者皆進行去質子化的作用機制。 除此之外，我們以菸醯苯胺（Nicotinanilide）對錯合物 DL25-A 及DL25-B 上的溴原子進行取代，發現其所得產物皆為 DL75，並且藉由晶體結構推測，DL25-A在反應過程中，會因周圍溶劑分子進行配位而導致結構產生重組。

Two rhenium(I) tricarbonyl complexes with 3-(2'-pyridyl)-1,2,4-triazole chelating ligand for anion sensing has been designed and synthesized. The identity and purity of these complexes have been characterized by NMR spectroscopy, mass spectrometry, and X-ray single-crystal diffraction. The complexes DL25-A and DL25-B are isomers to each other with the triazole ligand coordinating to Re(I) in different N-atoms. The anion sensing properties have been evaluated by UV-vis absorption, fluorescence, and 1H NMR titration experiments in acetonitrile. The absorption and fluorescence spectra for both complexes showed hypsochromic shifts upon addition of anions. The results of 1H NMR titration experiments have been confirmed that anion-receptor interaction is simple anion-induced deprotonation process. In addition, the same product, DL-75, was obtained upon replacing the Br atom on the complex DL25-A and DL25-B with nicotinanilide, which was confirmed by the crystal structure analysis. A structural re-orientation upon formation of the solvato-intermediate has been proposed to rationalize the reaction mechanism.