含羧酸與雙吡啶之銅配位聚合物的水熱合成、結構解析與性質研究

Hydrothermal Synthesis, Crystal Structures and Properties of Copper Coordination Polymers with Carboxylic acid and 4,4’-Trimethylene dipyridine

李元瀚(Yuan-Han Lee)

指導教授 ： 林嘉和

中原大學/理學院/化學系/碩士(2008年)

https://doi.org/10.6840/cycu200800226

摘要

本論文主要是以中溫水熱法合成具有孔洞性或特殊性質的銅的配位聚合物，並探討其結構化學與化合物的物理性質。而在本論文中依照所選用的不同種類的銅為中心金屬進行實驗並且區分為兩個部分。
第一個部分是以二水合氯化銅為起始物，合成出3個化合物，分別為：[CuICuIICl(bpp)2](BDC)(2.5H2O) (1) 、[CuICuIICl(bpp)2](mBDC)(2.5H2O) (2)及[CuICuIICl(bpp)2](H2BTEC)(H2O)(3)。這3個化合物都是由混價的CuICuIICl2這個四聚體作為一個連接中心並利用有機配位基4, 4’-trimethlene dipyridine連接這個四聚體而形成一個3D的金屬有機骨架化合物，而這橢圓形的管柱中填滿了有機羧酸陰離子及結晶水。
第二個部分是以三水合硝酸銅為起始物，並以4-4'-Trimethylene dipyridine(bpp)經由去氫耦合成的1,2,4,5-tetra(4-pyridyl)-benzene(TPB)為有機連接分子而合成出3個化合物，分別為：[Cu2(TPB)](BDC)(2.5H2O)(4)、[Cu2(TPB)](mBDC)(2.5H2O)(5)及[Cu2(TPB)](NB)2(2.5H2O)(6)。此3個化合物皆具有3D的骨架結構，但其孔洞內的陰離子是非序化的(disordered)，我們可藉由元素分析、熱重分析及紅外線光譜儀來鑑定此3個化合物孔洞中的陰離子及結晶水的數目。

關鍵字

中溫水熱法 ； 配位聚合物

並列摘要

In this , we use the middle temperature hydrothermal synthesis to prepare the Cu coordination polymers which have porous and special character, and discuss their structural chemistry and physical character. Two different Cu salts were used as starting materials and will be discussed in two section.
In section one , CuCl2．2H2O was used as starting material to synthesize three new coordination polymers, [CuICuIICl(bpp)2](BDC)(2.5H2O) (1) and [CuICuIICl(bpp)2](mBDC)(2.5H2O) (2) and [CuICuIICl(bpp)2](H2BTEC)(H2O)(3), all compounds adapt a 3-D metal-organic framework, where the mixed-valence CuICuIICl2 tetramer act connectors and the organic 4, 4’-trimethlenedipyridine as linkers. The oval- shaped columns are filled with organic carboxylate anions and lattice waters.
In section two , CuNO3．3H2O was used as starting material, and the linker is 1,2,4,5-tetra(4-pyridyl)-benzene (TPB) which was formed through the 4-4'-Trimethylenedipyridine (bpp) dehydrogenation coupling. Three new coordination polymers, [Cu2(TPB)](BDC)(2.5H2O)(4)、[Cu2(TPB)](mBDC)(2.5H2O)(5) and [Cu2(TPB)](NB)2(2.5H2O)(6), were obtained all three compounds have 3D frameworks and but the anions in the column were disordered. EA、TGA and IR were used to confirm the existence of anions and crystal water.

並列關鍵字

coordination polymers ； hydrothermal synthesis

參考文獻

1. S. Kitagawa, R. Kitaura, S.I.Noro, Angew. Chem. Int. Ed. 2004, 43,2334.

3. Adeline Y. Robin, Katharina M. Fromm, Coord. Chem. Rev 250 ,2006, 2127

4. R. Szostak, Molecular Sieves, Van Nostrand Reinhold, New York,

Nature, 2000, 404, 982.

6. Biradha, K.; Seward, C.; Zaworotko, M. J. Angew. Chem., Int. Ed.