含砒碇羧酸基之過渡金屬配位聚合物之結構分析與物性探討

Synthesis, Characterization and Physical Adsorption Properties for Coordination Polymers Synthsized from Transition-metal Ions and Carboxylate-Containing Pyridine

蔡長修(Chang-Shiou Tsai)

指導教授 ： 曾添文 ； 呂光烈

國立臺北科技大學/工程學院/化學工程研究所/碩士(2008年)

https://doi.org/10.6841/NTUT.2008.00539

摘要

本論文研究重點，在於將含 Pyridine 和羧酸基的L1、L2、L3 (L1 = 4-amino-3-[(pyridine-4-ylmethylene)-amino]-benzoic acid； L2 = 2-(4’-pyridineyl)-benzim-idazole-5-carboxylic acid； L3 = 2-(3’-pyridineyl)-benzi-midazole-5-carboxylic acid，分別與錳、鎘和鋅等兩價離子，利用室溫擴散自組裝合成法與水熱自組裝合成法，製備具有有機-無機金屬混成孔洞配位聚合物。

本論文探討所合成的5種有機-無機配位聚合物（metal-organic coordination polymer），分別為 [Mn(L2)2(H2O)4]•4H2O (1)、[Cd(L2)2(H2O)4]•4H2O (2)、[Zn(L3)4]•2(CH3OH)•12(H2O) (3)、[Zn(L3)4]•3(C6H6)•8(H2O) (4)、[Zn(L3)4]•2(C7H8)•
8(H2O) (5)。於論文中，將分為兩部分探討，第一部分的主題為各晶體在結構特性、熱穩定及其他物性上的鑑定分析;第二部分將針對化合物3~5對於水、苯、甲苯等客分子，進一步作吸附之分子辨認上的探討。

以L1配子和錳兩價離子所形成化合物[Mn(L2)2(H2O)4]•4H2O (1)，僅呈單體性的結構，且此結構和化合物[Cd(L2)2(H2O)4]•4H2O (2)的結構是相同的，只有在中心金屬的不同。以L3配子和鋅二價離子合成，得到二維孔洞的配位聚合物化合物[Zn(L3)4]•2(CH3OH)•12(H2O) (3)，由於在此結構中具有層狀的特性，在c軸方向視之，層與層之間相互堆疊，又進一步形成具有一維式的孔洞。在原結構，由c軸方向視之所呈現的孔洞並沒有任何客分子被捕捉吸附。因此，進一步著手進行孔道吸附客分子的特性，特別將化合物[Zn(L3)4]•2(CH3OH)•12(H2O) (3)浸於苯或甲苯的溶液中，分別得到含溶劑客分子的化合物[Zn(L3)4]•3(C6H6)•8(H2O) (4)與[Zn(L3)4]•2(C7H8)•8(H2O) (5)。在化合物[Zn(L3)4]•3(C6H6)•8(H2O) (4)中客分子苯在一維通道所排列的情況與化合物[Zn(L3)4]•2(C7H8)•8(H2O) (5)中的客分子甲苯是相似的。

關鍵字

超分子化學 ； 配位聚合物 ； 自組裝

並列摘要

In this thesis, three types of ligands, 4-amino-3-[(pyridine-4-ylmethylene)-amino]-benzoic acid (L1), 2-(4’-pyridineyl)-benzimidazole-5-carboxylic acid (L2) and 2-(3’-pyridineyl)-benzi-midazole-5-carboxylic acid (L3) were reacted with ZnII, MnII and CdII metal ions, respectively. Several metal–organic coordination polymers, [Mn(L2)2(H2O)4]•4H2O (1), [Cd(L2)2(H2O)4]•4H2O (2), [Zn(L3)4]•2(CH3OH)•12(H2O) (3), [Zn(L3)4]•3(C6H6)•8(H2O) (4), and [Zn(L3)4]•2(C7H8)•8(H2O) (5) were successfully synthesized.

The first part of this thesis will discuss the structures, thermal stability and physical properties of the products. The second part will focus on the adsorption properties of the 2D porous compound 3, which were examined using two guest molecules, toluene and benzene.

Results of single-crystal X-ray analysis reveal that compound 1 adopts a discretestructure. Compound 2 is an isostructure of compound 1. Compound 3 adopts a two-dimensional layer structure. No guest molecules were found between the layers of the structure. Specific guest molecules were successfully included in compound 3 by immersion of compound 3 in benzene or toluene to give compounds 4 and 5, respectively. The structures of 4 and 5 were characterized by single-crystal X-ray diffraction analysis.

並列關鍵字

supramolecule ； coordination polymers ； self-assembly

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