新式含氮橋基雙氮雜菲衍生之化合物合成、結構與性質研究

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Title:	新式含氮橋基雙氮雜菲衍生之化合物合成、結構與性質研究
Other Titles:	The new bis(1,10-phenanthrolin-2-yl)amine derivatives : synthesis, structure and properties
Authors:	張翔;Chang, Hsiang
Contributors:	淡江大學化學學系碩士班王文竹;Wang, Wen-Jwu
Keywords:	含氮橋基雙雜菲;酸解離常數;關聯性磁振頻譜;Bis(1,10-phenanthrolin-2-yl);Acid dissociation constant;COSY
Date:	2015
Issue Date:	2016-01-22 14:52:11 (UTC+8)
Abstract:	以1,10-二氮雜菲(1,10-phenanthroline)為基礎，所形成特殊類大環分子HDPA (bis(1,10-Phenanthrolin-2-yl)amine)的衍生物有別以往合成，L1。L1是與HDPA以往衍生物在不同氮上的取代，選擇其中一邊雜菲環上的外側氮加成而非在於橋雞氮上做取代，這樣的反應形成了一個不對稱的分子結構。而由於純化上替換陰離子所形成L2化合物。在L1以及L2的NMR光譜圖之間沒有太大差異，圖譜中由於不對稱性使得圖譜呈現許多個積分值為1的雙重峰，而且許多訊號峰有重疊情況難以判別因此利用二維的光譜技術，H-H COSY、HMQC及HMBC的方法來準確判別氫及碳的NMR光譜，並用ESI-MS確認其質量而確定是離子化合物以及有成功置換陰離子形成L2，並測量兩化合物的電化學性質。在酸鹼滴定實驗中，利用電子吸收光譜來偵測，經由計算後知道兩化合物的pKa值為3.31與2.98，並與起始物HDPA及橋基氮上取代衍生物做比較。並初步的測量兩化合物的電化學性質。這樣的結果是形成一個離子化合物，反應上有別於HDPA橋基氮上取代的簡易的反應程序以及最後的高產率。這樣的衍生物雖然與金屬上配位是不太可行的，但由於烷鏈末端是高反應性的碘，而有高反應性，在於衍生上還是有很大的可能。 In this research, new ionic compounds base on 1,10-phenanthroline, L1 and L2 were synthesized with high yield. L1 was synthesised by the reaction of macrocyclic molecule HDPA (bis(1,10-phenanthrolin-2-yl)amine) with 1,6-diiodohexane. The L1 was designed for different reaction site with HDPA derivatives synthesized in other research. L1 is synthesized by the modification of phenanthroline instead of bridge nitrogen of HDPA and generate an asymmetric structure. L2 was synthesized by the exchange of anion for the solubility. The H-H COSY, HMQC and HMBC technology were used for solving the aromatic signal of L1 and L2. And L1 and L2 were identified by ESI-MS. The acid titration UV-Vis experiments shows Pka of L1 was 3.13 and Pka of L2 was 2.98. The oxidation potential of L1 were -0.19 eV, -0.89 eV and L2 were -0.73 eV, -1.07 eV. The reduction otenrial of L1 were 0.68 eV, 0.93 eV and L2 were 0.76 eV, 0.88 eV.
Appears in Collections:	[Graduate Institute & Department of Chemistry] Thesis

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