臺灣博碩士論文加值系統

本文使用過渡金屬離子和 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole (4-bpt)經
由 自 組 裝 的 方 式 合 成 出 {[Cd(4-bdt)(atpa)(H2O)]·(DMF)(H2O)2}n (1),
{[Cd(4-bdt)(htpa)(H2O)]·DMF}n (2), {[Cd(4-bdt)(ntpa)(H2O)]·DMF}n (3),
{[Zn(4-bdt)(2,5-tdc)]·DMF}n (4), {[Zn(4-bdt)(cca)2]·DMAC}n (5),
{[Cu(4-bdt)2(H2O)]·(DMAC) (EtOH)0.5(H2O)3(NO3)2}n (6)等六個化合物，並以單晶
X-ray 繞射解析其結構，以螢光光譜法及氣體吸附實驗，探討各化合物的物理性
質。
鎘金屬離子和 4-bpt 配子於二甲基甲醯胺和水的混合溶劑中，分別與
2-aminoterephthalic acid (atpa) 、 2-hydroxyterephthalic acid (htpa) 或
2-nitroterephthalic acid (ntpa)以水浴法反應各得到化合物 1－3。化合物 1－3 為相
似的結構，都是以鎘金屬中心形成之二維平面，層與層間藉由氫鍵作用力形成三
維的超分子架構。化合物 1－3 中皆具有一維孔道，故進一步進行氣體吸附性質
之探討。
硝酸鋅金屬鹽類與 4-bpt 配子分別與 2,5-thiophenedicarboxylic acid (2,5-tdc)
或 4-carboxycinnamic acid (cca)兩種不同的羧酸根配子反應，各得到以鋅金屬離
子為基底的化合物 4 或 5，產物經由紅外線光譜、元素分析與單晶 X 光與粉末繞
射儀來鑑定結構，化合物 4 和 5 均為三維結構，其配位模式都非常類似於
paddle-wheel 的形式，兩個鋅金屬離子先與四個羧酸根上的氧原子配位，形成二
維的平面，再由 4-bpt 扮演著 pillar 的角色以氮原子與鋅金屬離子橋接而構成三
維的網狀結構，使化合物 4 和 5 都具有孔洞，此外化合物 4 和 5 都具有互穿的特
性，二氧化碳的氣體吸附性質也一併研究。
化合物 6 則以六配位之銅金屬中心形成二維平面，再透過氫鍵作用力及二次
互穿形成三維的超分子架構。

In this thesis, a series of supramolecular compounds and coordination polymers
were synthesized via self-assembly processes and their structures and properties were
examined.
Compounds {[Cd(4-bdt)(atpa)(H2O)]·(DMF)(H2O)2}n (1),
{[Cd(4-bdt)(htpa)(H2O)]·DMF}n (2), {[Cd(4-bdt)(ntpa)(H2O)]·DMF}n (3),
respectively, were produced by the reaction of cadmium salts,
4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole (4-bpt), and 2-aminoterephthalic acid (atpa),
2-hydroxyterephthalic acid (htpa) or 2-nitroterephthalic acid (ntpa) ligands in a mixture
of DMF/H2O at 50 °C. The structures of compounds 1, 2, and 3 are similar. They are
comprised of two-dimensional structures formed by seven-coordinated metal centers,
and three-dimensional supramolecular structures are formed by hydrogen bonding
interactions between the two-dimensional structures. Because the structure has a
one-dimensional channel, it has gas adsorption characteristics.
A series of zinc-based metal－organic frameworks {[Zn(4-bdt)(2,5-tdc)]·DMF}n
(4), {[Zn(4-bdt)(cca)2]·DMAC}n (5) were synthesized at 50 °C. The structures of the
two products were constructed from paddle-wheel units, which were formed from two
zinc ions, four carboxylates and two pyridine united. The properties of compounds 4
and 5 regarding the uptake of CO2 are also discussed.
The reaction of Cu2+ with 4-bpt in a mixture of DMAC/H2O/EtOH at room
temperature resulted in the formation of {[Cu(4-bdt)2(H2O)]·(DMAC)
(EtOH)0.5(H2O)3(NO3)2}n(6). Compounds 16 were characterized by infrared
spectroscopy (FT-IR), powder X-ray diffraction (PXRD), elemental analysis (EA),
and thermogravimetric analysis (TGA). Their structures were further confirmed by
single-crystal X-ray diffraction analysis.

目錄
摘要 i
Abstract iv
誌謝 v
目錄 vii
圖目錄 ix
表目錄 xiii
第一章 序論 - 1 -
1.1 超分子化學 - 1 -
1.2 超分子化學中作用力介紹 - 3 -
1.2.1 凡得瓦力 - 3 -
1.2.2 氫鍵 (hydrogen bonding) - 5 -
1.2.3 π－π堆疊作用力 (π－π stacking) - 6 -
1.3 金屬－有機配位聚合物 - 7 -
1.3.1 金屬－有機配位聚合物之構形種類 - 7 -
1.3.2 金屬－有機配位聚合物之構形設計 - 11 -
1.4 自組裝合成法 - 14 -
1.4.1 室溫自組裝－擴散法 - 14 -
1.4.2 水浴合成法 - 15 -
1.4.3 水熱合成法 - 15 -
1.5 配位聚合物對二氧化碳捕捉應用 - 17 -
第二章 實驗設計 - 20 -
第三章 實驗部分 - 23 -
3.1 儀器與藥品 - 23 -
3.1.1 儀器 - 23 -
3.1.2 藥品 - 24 -
3.2 有機配子之合成 - 25 -
有機配子4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole (4-bpt)的合成 - 25 -
3.3 金屬－有機配位聚合物的合成 - 26 -
3.3.1 鎘金屬與含4-bpt配子之金屬配位聚合物之合成 - 26 -
3.3.2 鋅金屬與含4-bpt配子之金屬配位聚合物之合成 - 29 -
3.3.3 銅金屬與含4-bpt配子之金屬配位聚合物之合成 - 31 -
第四章 結果與討論 - 32 -
4.1 化合物結構與物性的探討 - 32 -
4.1.1 化合物{[Cd(4-bdt)(atpa)(H2O)]•(DMF)(H2O)2}n (1)的結構描述及其性質分析: - 32 -
4.1.2 化合物{[Cd(4-bdt)(htpa)(H2O)]•(DMF)2}n (2)的結構描述及其性質分析: - 42 -
4.1.3 {[Cd(4-bdt)(ntpa)(H2O)]•X}n (3)的結構描述及其性質分析: - 54 -
4.1.4 {[Zn(4-bdt)(2,5-tdc)]•DMF}n (4)的結構描述及其性質分析: - 65 -
4.1.5 {[Zn(4-bdt)(cca)2]•DMAC}n (5)的結構描述及其性質分析: - 76 -
4.1.6 {[Cu(4-bdt)2(H2O)]•(DMAC)(EtOH)0.5(H2O)3(NO3)2}n (6)的結構描述及其性質分析: - 85 -
4.2 化合物1－6 之結構分析 - 93 -
4.2.1 化合物 1－3 之結構與物性討論 - 94 -
4.2.1 化合物4和5之結構與物性討論 - 97 -
第五章 結論 - 100 -
參考文獻 - 101 -
附錄 - 104 -

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