含嘧啶及咪唑有機配子之金屬有機配位化合物之自組裝合成、結構鑑定與性質研究

Self-assembly, Structures, and Properties of Metal—Organic Compounds with Pyrimidine and Imidazole Ligands

楊承翰(Cheng-Han Yang)

指導教授 ： 曾炳墝 ； 呂光烈

國立中正大學/理學院/化學暨生物化學系/碩士(2015年)

摘要

本論文分為兩個部分探討，第一部分為含pyrimidine配子1,2,3,6-tetrahydro-2,6-dioxo-4-pyrimidinecarboxylic acid (H2Or, orotic acid )與鈣及鈷金屬離子之水浴自組裝反應；第二部分為含imidazole配子 (E)-3-(1H-imidazol-4-yl)prop-2-enoic acid (HIA, urocanic acid )與鎘、鈷、鎳及鋅金屬離子之水浴自組裝反應，並研究得到的配位聚合物之結構與各項性質。
本實驗選用含羧酸基及分別含有imide及imidazole官能基之有機配子，由於有機配子具有多重官能基，故可能形成不同配位模式之化合物。
在第一部分中，化合物1為CaCl2與H2Or在80 ℃水浴條件下合成，得到一個三維配位聚合物{[Ca(Or)(H2O)]}n；化合物2為Co(NO3)2•6H2O與H2Or及4,4′-Bipyridine在50 ℃水浴條件下得到之零維單體化合物{[Co2(Or)2(bpy)(H2O)6]•H2O}。
在第二部分中，化合物3為Cd(NO3)2•4H2O與HIA及H2bdc (terephthalic acid)在80 ℃水浴條件下合成，得到三維配位聚合物{[Cd(IA)(bdc)0.5(DMF)]}n；化合物4、5為Co(NO3)2•6H2O和Ni(NO3)2•6H2O分別與HIA及H2bdc在80 ℃水浴條件下反應，其中H2bdc沒有參與配位，可得到{[Co(IA)2(H2O)4]}與{[Ni(IA)2(H2O)4]}兩個等結構零維單體化合物；化合物6、7為Zn(NO3)2•6H2O與HIA在80 ℃水浴條件下，一天後可得到三維配位化合物{[Zn(IA)2]•4H2O}n (6)
，有趣的是將無色透明的化合物6持續放在反應系統中六天後可得到淡黃色的化合物{[Zn(IA)2]•H2O}n (7)，兩者扣除客分子後為同分異構物；最後並加入其他不參與配位的無機鹽類來觀察化合物6轉變為7的影響。

關鍵字

配位聚合物 ； 自組裝

並列摘要

The goal of this study was to develop a self-assembly synthetic strategy for preparing coordination polymers using two ligands: orotic acid and urocanic acid. The synthetic method, structures and some properties of the products were investigated.
Because both of these ligands contain carboxylate, imide and imidazole functional groups, respectively, they offer a very rich coordination chemistry. Thus, the numerous binding modes of the ligands can be expected to give rise to materials with drastically differing structures.
The reaction of CaCl2•H2O with H2Or at 80 ℃ resulted in the formation of a 3D coordination polymer {[Ca(Or)(H2O)]}n (1); and the reaction of Co(NO3)2•6H2O with H2Or and 4,4′-bipyridine at 50 ℃ resulted in the formation of a 0D monomer
{[Co2(Or)2(bpy)(H2O)6]•H2O} (2).
The reaction of Cd(NO3)2•4H2O with HIA and H2bdc at 80 ℃ gave a 3D coordination polymer {[Cd(IA)(bdc)0.5(DMF)]}n (3), and, under the same conditions, but changing the metal ions to Co(NO3)2•6H2O and Ni(NO3)2•6H2O, two isostructure monomers {[Co(IA)2(H2O)4]} (4) and {[Ni(IA)2(H2O)4]} (5) are produced. The reaction of Zn(NO3)2•6H2O with HIA and KCl at 80 ℃ for 1 day gave a 3D coordination polymer {[Zn(IA)2]•4H2O}n (6). Interestingly, when transparent crystals 6 are allowed to stand in the reaction system for 6 days, they were transformed into a pale yellow compound {[Zn(IA)2]•H2O}n (7). Some non-coordinated salts like KF, KCl, KBr, NaCl can be added to control the time required for crystal transformation.
The structures of the seven coordination polymers were characterized by IR spectroscopy, elemental analysis and single-crystal or powder X-ray diffraction methods. The thermal stability of the products were examined by TGA.

並列關鍵字

coordination polymers ； self-assembly

參考文獻

1. Lehn, J.-M. Science 1985, 227, 849.

2. Lehn, J.-M. Angew. Chem. Int. Ed. Engl. 1988, 27, 90.

3. Pedersen, C. J. Angew. Chem. Int. Ed. Engl. 1988, 27, 1021.

4. Cram, D. J. Angew. Chem. Int. Ed. Engl. 1988, 27, 1009.

7. Gao, E. Q.; Liu, N.; Cheng, A. L.; Gao, S.; Chem. Commun. 2007, 24, 2470-2472.