含新型橋接配子之金屬－有機配位化合物之合成、結構鑑定與性質研究

Synthesis, Structures, and Properties of Metal-Organic Coordination Assemblies Containing Imide and Amine Based Bridging Ligands

張仲佑(Chung-Yu Chang)

指導教授 ： 吳景雲

國立暨南國際大學/科技學院/應用化學系/碩士(2012年)

摘要

本論文探討四個吲哚架構之雙官能基配子H2In4ba、H2In3ba、HIn4py與HIn4py，以及一個聯吡啶衍生配子bpmda自組裝合成配位聚合物之結構與物理性質。 本論文第一部分利用H2In4ba、H2In3ba、HIn4py及HIn4py與鋅、鎘及鋰金屬離子，在溶劑熱的條件下自組裝合成配位聚合物[Zn(In4ba)(py)2] (1)、[Cd(In4ba)(py)3]．1.5py (2)、[Li2(In3ba)(H2O)]．H2O (3)、[Cd1.5(btc)(py)4.5]．0.5(py) (4)與[Zn2(btec)(py)4] (5)。化合物1、2為一維結構，分別為螺旋狀及鋸齒狀，化合物3為二維層狀結構，化合物4為二維脊骨狀結構，其btc 配子於反應過程中由HIn4py或HIn3py水解生成，化合物5為二維斜方狀結構，其btec 配子於反應過程中由H2In3ba水解偶合重組而得。 第二部分以化合物1經高溫處理後使吡啶分子脫去產生化合物[Zn(In4ba)]n (1’)，再進行其對吡啶、乙腈、水及2,2’-bipyridine等分子之吸附。實驗結果顯示1’可吸附吡啶分子並回復至1之堆疊特性。此外，1’對水分子，2,2’-bipyridine分子亦有一定程度的吸附效果，但無法吸附乙腈分子。 本論文最後利用bpmda與銅金屬離子，在室溫自組裝下製得三種不同型態之產物[Cu(bpmda)](NO3) (6)、[Cu(bpmda)Cl]Cl．3.25H2O (7)、[Cu(H2bpmda)(H2O)4](SO4)2．2(H2O) (8)。化合物6為一維梯子狀結構，化合物7為一維格子狀結構，化合物8為一維鋸齒狀結構。

關鍵字

自組裝 ； 水(溶劑)熱 ； 配位聚合物 ； 金屬－有機骨架

並列摘要

The goal of this study is to develop a self-assembly synthetic strategy for the preparation of coordination polymers using isoindoline-based ligands, 2-(4-carboxyphenyl)-1,3-dioxoisoindoline-5-carboxylic acid (H2In4ba),
2-(3-carboxyphenyl)-1,3-dioxoisoindoline-5-carboxylic acid (H2In3ba),
2-(4-pyridyl)-1,3-dioxoisoindoline-5-carboxylic acid (HIn4py), and
2-(3-pyridyl)-1,3-dioxoisoindoline-5-carboxylic acid (HIn4py), and bipyridine-based ligand N,N'-bis(3-pyridylmethyl)-1,2-diaminoethane (bpmda).

Several coordination complexes, [Zn(In4ba)(py)2] (1), [Cd(In4ba)(py)3]．1.5py (2), [Li2(In3ba)(H2O)]．H2O (3), [Cd1.5(btc)(py)4.5]．0.5(py) (4), [Zn2(btec)(py)4] (5), [Cu(bpmda)](NO3) (6), [Cu(bpmda)Cl]Cl．3.25H2O (7) and [Cu(H2bpmda)(H2O)4](SO4)2．2(H2O) (8) were successfully synthesized. Complexes 1 and 2 adopt a 1-D helical chain structure and a 1-D zigzag structure, respectively, whereas complexes 3-5 adopt a 2-D layer structure, a 2-D herringbone structure, and a 2-D rhombus grid structure, respectively. Complexes 6-8 exhibit a 1-D ladder-like chain structure, a 1-D grid chain structure, and a 1-D zigzag chain structure, respectively.
The adsorption feature of solvent-free sample of [Zn(In4ba)]n (1’) has been studied. Immersing 1’ in pyridine, water, acetonitrile, and dichloromethane solution of 2,2’-bipyridine results that 1’ is capable of adsorbing py, H2O, and 2,2’-bipy, but it does not show the adsorption behavior to the CH3CN molecules.

Finally, this thesis describes structures, thermal stability, and physical properties of the complexes 6-8. All the three complexes exhibit 1-D chain structures, but in different manners that a ladder-like chain for 6, a grid chain for 7, and a zigzag chain for 8.

並列關鍵字

Self-Assembly ； Hydro(solvo)thermal ； Coordination Polymer ； Metal－organic frameworks

參考文獻

1. Lehn, J. M. Science 1985, 227, 849-856.

2. Lehn, J. M. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 4763-4768.

3. Lehn, J. M. Nobel lecture 1987.

4. Cram, D. J. Angew. Chem., Int. Ed. Engl. 1988, 27, 1009-1020.

5. Holliday, B. J.; Mirkin, C. A. Angew. Chem., Int. Ed. 2001, 40, 2022-2043.