含哌嗪或三氮唑配子之配位聚合物的自組裝合成、結構與性質研究

Self-assembly, Structures, and Properties of Coordination Polymers Based on Piperazine or Triazole Ligand

蘇崇誠(Chong-Cheng Su)

指導教授 ： 曾添文 ； 呂光烈

國立臺北科技大學/工程學院/化學工程研究所/碩士(2012年)

摘要

本論文分兩部分
(一) 水熱自組裝合成含pyridine與carboxylate之配位聚合物：
利用4,4’-dipyridylpiperazine (dpyp)和三種羧酸配子與鈷金屬離子，進行水熱自組裝合成，得到配位聚合物 1－4。以L-aspartic acid配子反應得到{[Co(dpyp)1.5(C3H6NO2)Cl]•Et2O•DMF}n (1)，以L-tartaric acid配子反應得到[Co(dpyp)Cl2]n (2)，以2,4-pyridinedicarboxylic acid配子反應得到{[Co4(2,4-pydc)4(H2O)10]}n (3) 及{[Co(dpyp)(H2O)4][Co(2,4-pydc)2(H2O)2]}n (4)，若與鎳離子反應，則得到[Ni(2,4-pydc)(H2O)4] (5)。在第一部分共得到五個配位化合物，探討其結構及熱穩定性，並討論數種不同的羧酸配子對各項性質之影響。
(二) 室溫自組裝合成配位錯合物：
利用3-amino-1H-1,2,4-triazole-5-carboxylic acid (atzc)，分別與銦與鐵離子，以室溫擴散方式進行自組裝合成配位化合物6－7，與氯化銦反應得到配位化合物[Et3NH][In(atzc)4]•H2O (6)，與硝酸亞鐵反應得到化合物[Fe(atzc)2(OH)]•4(H2O) (7)。第二部分得到兩個化合物，討論化合物之結構，並探討其具推拉電子效應對放光性質與介電性質之影響。

關鍵字

自組裝，配位化合物 ； 過渡金屬 ； 含哌嗪配子 ； 含三氮唑配子

並列摘要

(1) Synthesis of coordination polymers under hydrothermal conditions :
The treatment of transition-metal ions (CoII,NiII) with 4,4’-dipyridylpiperazine (dpyp) ligand and three kinds of carboxylic acid ligand (L-aspartic acid, L-tartaric acid, 2,4-pyridinedicarboxylic acid) in aqueous solution under hydrothermal conditions, leds to the formation of coordination polymers 1－5. We have successfully synthesized five complexes {[Co(dpyp)1.5(C3H6NO2)Cl]•Et2O•DMF}n (1), [Co(dpyp)Cl2]n (2), {[Co4(2,4-pydc)4(H2O)10]}n (3), {[Co(dpyp)(H2O)4][Co(2,4-pydc)2(H2O)2]}n (4), [Ni(2,4-pydc)(H2O)4] (5).
Compounds 1－3 are 1D chain structures. The structure of compound 4 is comprised of 1D chains structure and accompied with discrete monomers. Compound 5 is a monomer. Compounds 3 and 4 are obtained by adjusting the pH values of the basic solvent used.

(2) Self-assembly of metal-organic complex under room temperature :
Treatment of 3-amino-1H-1,2,4-triazole-5-carboxylic acid (atzc) with metal ions (InIII and FeIII) under room temperature, leads to the formation of complex [Et3NH][In(atzc)4]•H2O (6) and [Fe(atzc)2(OH)]•4(H2O) (7), respectively.
The structures of compounds 6 and 7 are 0D monomer. Compound 6 possesses a asymmetric space group (I222). The dielectric properties and emission properties of 6 were studied.

並列關鍵字

self-assembly ； coordination polymer ； transition metal ； piperazine ligand ； triazole ligand

參考文獻

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