含哌嗪與羧酸配位聚合物之自組裝合成、結構及性質探討

Combination of Piperazine and Carboxylate Ligands toward the Design of Metal-Organic Frameworks

林建文(Jian-Wen Lin)

指導教授 ： 賴榮豊

共同指導教授 ： 呂光烈(Kuang-Lieh Lu)

國立暨南國際大學/科技學院/應用化學系/碩士(2009年)

摘要

本論文探討以含彎曲性哌嗪(piperazine)配子4,4’-dipyridylpiperazine (2N-DPyP)搭配各種堅固或彎曲性羧酸根配子與過渡金屬離子之水熱自組裝合成反應，並研究得到的配位聚合物結構與各項性質。
本實驗為選用不同的角形羧酸根配子4,4’-(Hexafluoro isopropylidene) diphthalic anhydride (6FDA)、Benzophenone-3,3’,4,4’-tetracarboxylic dianhydride (BPTDA)、4,4’-
Oxydiphthalic anhydride (ODA)，由於中心具有三種不同形式的官能基，故在與金屬離子參與配位時具有相當大的多變性。
本論文分為三個部分進行討論， 第一部分選用結構較堅硬的1,2,4,5-tetra carboxylates 與含吡嗪配子自組裝生成一維配位聚合物{[Co(betc)(H2O)4] ．(2N-DPyP)0.5(H2O)}n (1)、{[Ni(betc)(H2O)4]．(2N-DPyP)0.5(H2O)}n (2)。
第二部份選用具彎曲性羧酸根配子與含吡嗪配子自組裝生成三維配位聚合物{[Ni2(2N-DPyP)2(6FDT)(H2O)2]．(2N-DPyP)2.5(H2O)}n (3)、{[Cd2(2N-DPyP)2(BPTC)(H2O)2]．0.5(H2O)}n (4)、[Ni2(2N-DPyP)2(ODT)(H2O)2]n (6)及二維配位聚合物[Ni3(2N-DPyP)3(HODT)2(H2O)9]n (5)。
第三部分綜合比較各種反應條件對含吡嗪配子與不同構型之羧酸根自組裝合成之影響。
本研究詳細探討各化合物實驗合成方法、結構解析，並測量其熱穩定及光物理性質，並對可彎曲性哌嗪基團及彎曲性羧酸根基團之結構變化及構形差異做深入探討。

關鍵字

配位聚合物 ； 自組裝 ； 含哌嗪吡啶配子 ； 彎曲性羧酸配子

並列摘要

This thesis describes the self-assembly of a flexible 4,4’-dipyridylpiperazine (2N-DPyP) and rigid or flexible carboxylate ligands and metal ions. The synthetic method, structures and photophysical properties of the products were investigated.
Carboxylate including 4,4’-(hexafluoro isopropylidene)diphthalic anhydride (6FDA), benzophenone-3,3’,4,4’-tetracarboxylic dianhydride (BPTDA), 4,4’-oxydiphthalic anhydride (ODA) were employed in the present investigation. Due to three different kind of functional space groups, the metal ions coordinated to the ligands in different modes.
The first part of this thesis describes the self-assembly of 1D coordination polymers, such as {[Co(betc)(H2O)4]．(2N-DPyP)0.5(H2O)}n (1), {[Ni(betc)(H2O)4]．(2N-DPyP)
0.5(H2O)}n (2) from non-flexible 1,2,4,5-tetra carboxylate and piperazine ligands.
The second part describes the preparation of 3D coordination polymers, {[Ni2(2NDPyP) 2(6FDT)(H2O)2]．(2N-DPyP) 2.5(H2O)}n (3), {[Cd2(2N-DPyP)2(BPTC)(H2O)2]．0.5(H2O)}n (4), [Ni2(2N-DPyP)2(ODT)(H2O)2]n (6) and a 2D coordination polymer, [Ni3(2N-DPyP)3(HODT)2(H2O)9]n (5), which are self-assembled from flexible carboxylate andpiperazine ligands.
The third part describes different experimental procedure of the self-assembling synthetic strategy employing piperazine and carboxylate ligands.
In this study, the synthetic strategies, X-ray structural characterization, thermal stability and photophysical properties of the synthesized coordination polymers were carried out.
Structural variation, particularly differences in piperazine and flexible carboxylate conformation, makes these metal-organic frameworks interesting supramolecules.

並列關鍵字

coordination polymers ； self-assembly ； piperazine ； flexible carboxylate

參考文獻

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