超分子配位聚合物自組裝與分子結構之研究

Study on Self-assembly and Molecular Structure of Supramolecular Coordination Polymers

李錦祥(Gene-Hsiang Lee)

指導教授 ： 王賢達

國立臺北科技大學/工程學院/工程科技研究所/博士(2007年)

摘要

近年來超分子配位聚合物(supermolecular coordination polymer)的設計、自組裝合成與應用被受矚目，設計不同幾何形狀與角度的有機配基和金屬離子的來做自組裝，將可組裝出多種不同結構且具有某些特定功能的超分子配位聚合物。本論文研究選擇的金屬離子有Co+2、Ni+2、Cu+2、Zn+2和Cd+2，有機配基則選擇自行設計開發新的配基或是文獻已報導的配基兩大類。 在本文中我們自行設計開發五種新的pyrazine-modulated N,N′-bis(α-pyridyl)- 2,6-diaminopyridine有機配基 [(N-Pyrazin-2-yl)(N′-pyridin-2-yl)pyridine-2,6-diamine (H2pzpypy)、N,N′-Bis(pyridin-2-yl)pyrazine-2,6-diamine (H2pypypz)、(N-Pyrazin- 2-yl)-(N′-pyridin-2-yl)pyrazine-2,6-diamine (H2pzpypz)、N,N′-Bis(pyrazin-2-yl)- pyridine-2,6-diamine (H2pzpzpy)和N,N′-Bis(pyrazin-2-yl)pyrazine-2,6-diamine (H2pzpzpz)]，和過渡金屬Cu+2和Ni+2自組裝，經由X光單晶繞射分子結構分析，獲得數個一維、二維、三維超分子配位聚合物，並研究討論TGA熱重分析和磁性性質。 另外也合成一種新穎含三唑基團並具雙配位性質的配基，trans-4,4'-azo-1,2,4- triazole (atr)，此配基是藉由偶氮連接兩端的三唑基團形成一共平面結構，兩端的三唑基團都具有配位性質，因此成為合成多維配位聚合物的理想配基。我們藉由不同比例的反應條件或者混搭其他配基方式，順利合成出1-D、2-D 以及3-D的Co(II)配位聚合物。 已報導的配基我們選擇1,4-bis(3-pyridyl)2,3-diaza-1,3-butadiene (3-bpd)，成功獲得三個配位聚合物，其一為有著相同構築單元確有著不同構形的一維[ZnCl2(3-bpd)]n配位聚合物，經由X光單晶繞射分子結構分析顯示，一為維螺旋鏈狀結構，另一為方波形鏈狀結構，而兩個結構都以C−H•••Cl分子間氫鍵將鏈狀分子相連接，形成三維的配位聚合物；另一配位聚合物則是[Ni2(NO3)4(3-bpd)3]n•nEtOH，所有3-bpd當架橋配基，連接相隣Ni原子形成三維結構，在這三維結構中產生大小約6.7x8.5Å沿著a軸的一維微孔洞，而乙醇分子被吸附在此孔洞內。 另一已報導的配基我們選擇N,N′-Bis(4-pyridylmethyl)oxalamide (4py-ox)，自組裝出兩個配位聚合物，其一為[CoCl2(4py-ox)]n•0.5nH2O配位聚合物，為一維鋸齒鏈狀的結構，而兩條一維鋸齒鏈以前後交錯的方式堆疊，形成一大小約為8.6 × 8.6 Å2正方形的通道，水分子以氫鍵與4py-ox鍵結存在具通道內。另一為 [Cd(NO3)2(4py-ox)1.5]n二維配位聚合物，但此二維配位聚合物在立體結構上以相互交錯的方式來堆疊，所以並沒有得到很好的孔洞結構。

關鍵字

超分子，配位聚合物，自組裝，X光分子結構。

並列摘要

In recent years, the design, self-assembly, and application of supramolecular coordination polymers have been extensively studied. The organic ligands with different geometry shape and angle have been designed and synthesized. The reactions of these organic ligands with the metallic ions form the corresponding functional coordination polymers. In this dissertation, the metallic ions were chosen from Co+2, Ni+2, Cu+2, Zn+2 and Cd+2. Two types of the organic ligands were selected for self-assembly. One type of ligand was based on literature synthesized, the other type of ligand was designed and synthesized.

We synthesized five new pyrazine-modulated ligands, [(N-Pyrazin-2-yl)(N'-pyridin-2-yl)pyridine-2,6-diamine (H2pzpypy), N,N'-bis(pyridin- 2-yl)pyrazine-2,6-diamine (H2pypypz), (N-Pyrazin-2-yl)-(N'-pyridin-2-yl)pyrazine- 2,6-diamine (H2pzpypz), N,N'–bis(pyrazin-2-yl)-pyridine-2,6-diamine (H2pzpzpy) and N,N'–bis(pyrazin-2-yl)pyrazine-2,6-diamine (H2pzpzpz). By coordinating with metal ions Cu+2 and Ni+2, several 1-D, 2-D and 3-D supramolecular coordination polymers determined by X-ray single crystal diffraction have been obtained.

Another new ligand, trans-4,4'-azo-1,2,4-triazole (atr) was also synthesized for the construction of coordination polymers. The ligand is a planar molecule with two triazoles linked by an azo group. It could be served as a multi-dentate ligand or a good linkage ligand. A series of Co(II) polymeric compounds with 1-D, 2-D and 3-D frameworks have been successfully synthesized and characterized structurally.

The ligand, 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (3-bpd), has also been used for the synthesis of three novel coordination polymers. Two novel coordination polymers have the same chemical composition, [ZnCl2(3-bpd)]n and they show different structural conformations with one forming a helical chain and the other a square-wave chain. The intermolecular C−H•••Cl hydrogen bonds in both structures play important roles in the formation of 3-D framework. The coordination polymer [Ni2(NO3)4(3-bpd)3]n•nEtOH, with all the bridging ligands in a bis-monodentate mode connecting to the Ni(II) ions, formed a 3-D metal-organic polymeric framework that shows a 1-D microporous channel with dimensions of ca. 6.7 x 8.5 Å2 along the a-axis. The EtOH guest molecules are intercalated into these channels.

The reaction of N,N'-bis(4-pyridylmethyl)oxalamide (4py-ox) with Co+2 and Cd+2 formed two novel supramolecular coordination compounds, [CoCl2(4py-ox)]n•0.5nH2O, and [Cd(NO3)2(4py-ox)1.5]n, respectively. The structure of [CoCl2(4py-ox)]n•0.5nH2O features a 1-D zigzag chain. Two interwoven chains create a cavity of ca 8.6 x 8.6 Å2, which produces a 3-D channel and water molecules are held in the channel by hydrogen bonds. The structure of [Cd(NO3)2(4py-ox)1.5]n shows a 2-D sheet polymeric framework and the neighboring sheets are interlaced, and the 3-D structure of this compound is microporous.

並列關鍵字

Supramolecule, Coordination polymer, Self-assembly, X-ray molecular structure.

參考文獻

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