溶劑調控互穿之金屬有機配位聚合物: 自組裝合成、結構鑑定與性質研究

Solvent Controlled Interpenetrating Metal-Organic Framework: Self-assembly, Structures, and Properties

王祥豪(Shiang-Hau Wang)

指導教授 ： 曾添文

共同指導教授 ： 呂光烈

國立臺北科技大學/工程學院/化學工程研究所/碩士(2014年)

摘要

本研究中分成兩個部分，第一部分為使用含有tetrazole官能基的1H-tetrazole-5-acetic acid (H2Tza) 有機配子與銅金屬離子自組裝反應，合成得到有機配位聚合物{[Cu5(CHN4)9]·Cl}n (1)，鑑定其結構並探討其性質；第二部分利用2-cyano-3-(pyridin-4-yl)acrylic acid有機配子與過渡金屬離子(Zn2+ Cd2+ Cu2+)，進行自組裝合成配位聚合物2‒5，並鑑定結構及研究其性質。
第一部份:
氯化銅與H2Tza以水為溶劑進行水熱法合成，得到三維的配位聚合物{[Cu5(CHN4)9]·Cl}n (1)，經單晶X-ray繞射解析，發現該化合物具有一維孔道的蜂窩狀結構。
第二部份:
化合物2‒5，皆以有機配子2-cyano-3-(pyridin-4-yl)acrylic acid與過渡金屬進行反應之產物。其中在室溫分層法的條件下，與硝酸銅合成得到化合物{[Cu(C9H5N2O2)2(DMF)]}n (2)；與過氯酸鋅自組裝合成得到化合物{[Zn3(C9H5N2O2)6]}n (5)。另外同樣以2-cyano-3-(pyridin-4-yl)acrylic acid作為有機配子，於50 °C下反應，與氯化鋅合成得到化合物{[Zn(C9H5N2O2)2(H2O)]}n (3)，與硝酸鎘反應可合成得到{[Cd(C9H5N2O2)2(H2O)]}n (4)。經單晶X-ray繞射解析顯示，化合物2為二維的層狀結構；化合物3與化合物4都是五次互穿的三維鑽石型結構；化合物5為三次互穿的鑽石型結構。其中，化合物3和4的結構屬於非中心對稱的空間群。
本論文中，共合成出5個金屬‒有機配位聚合物，其中化合物2‒5中，發現當合成時，經由溶劑的些微調控，可分別得到不同互穿維次的結構。最後個皆經由紅外線吸收光譜、元素分析及單晶、粉末X-ray繞射解析作結構鑑定，並測定其相關性質。

關鍵字

自組裝 ； 配位聚合物 ； 鑽石型結構 ； 孔洞材料

並列摘要

In this thesis, my research mainly focused on the following two parts.
(1) Self-assembled coordination compound using 1H-tetrazole-5-acetic acid ligand.
Treatment of the organic 1H-tetrazole-5-acetic acid ligand (where the tetrazole moiety possesses a five-membered heterocyclic group with four N donors) with copper (II) ions under hydrothermal conditions at 160 °C afforded compound {[Cu5(CHN4)9]·Cl}n (1). Condutions for its preparation and the structures of the product were investigated.
(2) Self-assembled coordination compounds using 2-cyano-3-(pyridin-4-yl)acrylic acid ligand.
Reactions of transition-metal ions with the ligand 2-cyano-3-(pyridin-4-yl) acrylic acid ligand were carried out under mild reaction conditions, resulting in the production of four coordination polymers. Compound {[Cu(C9H5N2O2)2(DMF)]}n (2) and compound {[Zn3(C9H5N2O2)6]}n (5) were synthesized at room temperature. Compound 2 is a two-dimensional layered coordination polymer, while compound 5 is a three-dimensional coordination polymer. Compounds {[Zn(C9H5N2O2)2(H2O)]}n (3)、{[Cd(C9H5N2O2)2(H2O)]}n (4) and compound {[Zn3(C9H5N2O2)6]}n (5) are 3D coordination polymers with different interpenetration dia topologies and were synthesized by a solvent controlled method.
The structures of the five compounds were characterized by single-crystal X-ray diffraction, Infrared spectroscopy, Thermogravimetry analysis, elemental analysis and powder X-ray diffraction methods. The emissions and non-linear optical (NLO) properties of compounds 3 and 4 were investigated.

並列關鍵字

acentric coordination polymers ； metal‒organic framwork ； porous meterials ； self-assembly

參考文獻

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

4. Desiraju, G. R. Nature 2001, 412, 397-400.

5. Lehn, J. M. Angew. Chem., Int. Ed. 1988, 27, 89-112.

6. Pedersen, C. J. Angew. Chem., Int. Ed. 1988, 27, 1021-1027.

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