具哌嗪配位聚合物之自組裝、結構及光物理性質

Self-assembly, Structures and photophysical properties of piperazine-containing coordination polymers

李瑾棻(chin-fen Li)

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(2006年)

https://doi.org/10.6837/NCNU.2006.00017

摘要

本論文探討兩種可彎曲性哌嗪（piperazine）配子 – 4,4’-dipyridylpiperazine（2N-DPyP）及N,N’-dipyraziylpiperazine（4N-DPzP）自組裝合成配位聚合物之調控，結構與光物理性質。
本論文分為三大部分，分別以2N-DPyP或4N-DPzP單一配子與金屬離子於室溫下進行擴散合成配位聚合物，及4N-DPzP混合其他配子與金屬離子行水熱法合成。
第一部分以2N-DPyP配子與較大原子半徑之汞離子自組裝反應生成配位聚合物[Hg(2N-DPyP)(CN)2]n (1)，藉由配子間之作用力造成汞原子規則排列形成一金屬線，具有特殊之光物理性質。
第二部份選用金屬銀、鎳或銅離子與4N-DPzP配子自組裝合成一維配位聚合物[Ag(4N-DPyP)(NO3)]n (2)、[Ni(4N-DPzP)3(NO3)2]n (3)及二維配位聚合物[Cu(4N-DPzP)2(NO3)2(THF)]n (4)。先前研究室以4N-DPzP與含不同陰離子（BF4－、SbF6－及PF6－）之銀鹽反應已合成一系列化合物，本篇則選用分子較小、配位能力較強的硝酸根離子進行類似反應，並和先前結果比較，討論陰離子對自組裝產物結構配位及排列的影響。
第三部份以鎘金屬離子及4N-DPzP配子為主體，加入不同配子（benzene-1,4- dicarboxylic acid (BDA)及benzene-1,2,4,5-tetracarboxylic acid (btec)），合成出二維配位聚合物[Cd2(4N-DPyP)2(BDA)2(H2O)1]n (5)及三維配位聚合物[Cd2(4N-DPyP)( btec)]n (6)。
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（piperazine）基團之結構變化及構形做深入探討。

關鍵字

超分子化學 ； 哌嗪衍生物 ； 自組裝 ； 配位聚合物 ； 晶體結構

並列摘要

The goal of this study was to develop a self-assembly synthetic strategy for the preparation of coordination polymers using piperazine derivatives, 4,4’-dipyridlpiperazine (2N-DPyP) and N,N’-dipyraziylpiperazine (4N-DPzP), as flexible ligands. The synthetic method, the structures and photophysical properties of the products were investigated.
The first part of this thesis describes the self-assembly of a 1D polymer, [Hg(2N-DPyP)(CN)2]n (1), from the reaction of mercury cyanide and 2N-DPyP ligand. An unusual photophysical properity of 1 was observed.
The second part of the thesis reports on the preparation of 1D polymers, [Ag(4N-DPyP)(NO3)]n (2), [Ni(4N-DPzP)3(NO3)2]n (3), and a 2D polymer, [Cu(4N-DPzP)2(NO3)2(THF)]n (4), assembled from 4N-DPzP and silver nitrate, nickel nitrate, and copper nitrate, respectively. The anion effect was found to play a key role in controlling the topologies of the final products.
The third part describes the preparation of a 2D coordination polymer, [Cd2(4N-DPyP)2(BDA)2(H2O)1]n (5), and a 3D compound, [Cd2(4N-DPyP)( btec)]n (6). The products were assembled from cadmium perchlorate and 4N-DPzP along with other ligands i.e. benzene-1,4-dicarboxylic acid (BDA) and benzene-1,2,4,5-tetracarboxylic acid (btec).
In this study, the synthetic strategies, structural characterization, thermal stability and photophysical properties of the synthesized coordination polymers were examined. Structural variation, , particularly differences in piperazine conformation and photophysical properties, make these metal-organic frameworks interesting supramolecules.

並列關鍵字

piperazine ； self-assembly ； coordination polmers ； structure ； photophysical property

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