鎳、鈷、銅金屬離子與吡啶-羧酸混配子 自組裝合成配位聚合物之研究

Design of Inorganic-Organic Hybrid Materials Based on Pyridine and Carboxylate Mixed Ligands

許良平(Liang-Ping Shu)

指導教授 ： 李光華 ； 呂光烈

國立中央大學/理學院/化學系/碩士(2006年)

摘要

中文摘要
本論文研究重點在於探討混配子(吡啶和羧酸衍生物)和金屬陽離子(Ni2+、Co2+、Cu2+) 經水熱反應得到一系列配位聚合物之結構與性質。
本文針對有機配子的組合型式，區分為兩種類型。第一類型是以2,6-naphthalenedicarboxylic acid (2,6-H2ndc)和 4,4’-bipyridine (4,4’-bpy) 或 trans-1,2-bis(4-pyridyl)ethylene (bpe) 為混配子，分別與鎳、鈷金屬的鹽類在水熱條件下反應，分別得到各化合物[{Ni(2,6-ndc)(4,4’-bpy)1/2}]n (1)、 [{Co(2,6-ndc)(4,4’-bpy)1/2}]n (2)、 [{Ni (2,6-ndc)(bpe)H2O}]n (3)、 [{Co2(2,6-ndc)2(bpe)}3．H2O]n (4)。單晶X-ray繞射鑑定分析顯示1、2為等結構化合物，具有特殊的互穿結構。第二類型則是以benzene-1,3,5-tricarboxylic acid (1,3,5-H3btc)和4,4’-dipyridylpiperazine (2N-DPyP) 為混配子，與銅、鎳金屬的鹽類反應，分別得到化合物[{Cu(1,3,5-btc)} (2N-DPyPH2)1/2‧2H2O]n (5)、 [{Ni(1,3,5-btc)(2N-DPyPH)(2N-DPyP)1/2(H2O)}‧H2O]n (6)、 [{Ni3(1,3,5-btc)2 (2N-DPyP)3(H2O)2}‧2H2O]n (7)。而化合物6、7的產率可由溶液pH值和金屬配子比例而調控。

關鍵字

超分子 ； 配位聚合物

並列摘要

Abstract
The self-assembly of Ni2+, Co2+ or Cu2+ ions with pyridine and carboxylate mixed ligands under hydrothermal conditions afforded a series of coordination polymers. The solid state structures of the products were characterized by single-crystal X-ray diffraction analyses.
Treatment Ni2+ or Co2+ ions with mixed ligands of 2,6-naphthalenedicarboxylic acid (2,6-H2ndc) and 4,4’-bipyridine (4,4’-bpy) or trans-1,2-bis(4-prydyl)-ethylene (bpe) under hydrothermal conditions gave compounds [{Ni(2,6-ndc)(4,4’-bpy)1/2}]n (1)、 [{Co(2,6-ndc)(4,4’-bpy)1/2}]n (2)、 [{Ni (2,6-ndc)(bpe)H2O}]n (3) and [{Co2(2,6-ndc)2(bpe)}3．H2O]n (4), respectively. Single-crystal X-ray diffraction analyses reveals that compound 1 and 2 are isostructures with interpenetrated architectures. Reaction of Ni2+ ion with benzene-1,3,5-tricarboxylic acid (1,3,5-H3btc) and 4,4’-dipyridylpiperazine (2N-DPyP) via hydrothermal method produced compounds [{Ni(1,3,5btc)(2N-DPyPH)(2N-DPyP)1/2(H2O)}‧H2O]n (6) and [{Ni3(1,3,5-btc)2(2N-DPyP)3(H2O)2}‧2H2O]n (7). Under similar reactions, Cu2+ reacted with 1,3,5-H3btc and 2N-DPyP to form [{Cu(1,3,5-btc)}(2N-DPyPH2)1/2‧2H2O]n (5). However, the yield of compounds 6 and 7 could be tuned by changing the pH value and the metal to ligand ratio in the solution.

並列關鍵字

supramolecule ； coordination polymer

參考文獻

1. Meijer, E. W. Chem. Rev. 2005, 105, 1491.

2. Choi, E. Y.; Kwon, Y. U. Inorg. Chem. 2005, 44, 538.

3. Meijer, E. W. Chem. Rev. 2001, 101, 4071.

4. Moulton, B.; Michael, J. Chem. Rev. 2001, 101, 1629.

6. Ehrlich, P. Studies on Immunity, Wiley, New York. 1906.