含1,4-二(磷酸亞甲基)-2,3,5,6-四甲基苯配子配位聚合物之自組裝

Self-assembly, Structures, and Properties of 1,4-Bis(methylene phosphonic acid)-2,3,5,6- tetramethylbenzene Containing Coordination Polymers

葉臻(Zhen Yeh)

指導教授 ： 呂光烈 ； 曾添文

國立臺北科技大學/工程學院/化學工程研究所/碩士(2013年)

摘要

本文研究為二磷酸基的有機配子1,4-bis(methylene phosphonic acid) 2,3,5,6-tetramethylbenzene (H4bmpb)與過渡金屬離子 (CoII、MnII)和鹼土族離子(BaII)，在調控的酸鹼及溫度環境下，進行自組裝合成，製備有機-無機金屬之配位聚合物。

以H4bmpb與過渡金屬離子(MnII、CoII)與鹼土族離子(BaII)利用室溫反應方式，在調控pH值下，得到兩個相類似結構的一維鍊狀配位聚合物 {[Co(H2bmpb)(H2O)4]•2H2O}n (1)、{[Mn(H2bmpb)(H2O)4]•2H2O}n (2)，及得到一個共結晶複合物{[Ba2(H2O)12•(bmpb)]•4H2O} (3)，一併探討其結構特性與物性分析。利用H4bmpb與過渡金屬離子(CoII)分別與4,4'-bipyridine配子及2,2'-bipyridine配子進行自組裝合成。利用室溫下反應，得到二維平面結構{[Co(H2bmpb)(4,4-bpy)(H2O)2]•2H2O}n (4)，及在恆溫60℃得到一維鍊狀配位聚合物 {[Co(H2bmpb)(2,2-bpy)(H2O)2]•2H2O}n (5)，最後一併探討其結構特性與物性分析。

關鍵字

配位聚合物 ； 磷酸基配位分子 ； 自組裝

並列摘要

In this thesis, a bis-phosphonate acid ligand 1,4-bis(methylene phosphonic acid) 2,3,5,6-tetramethylbenzene (H4bmpb) was reacted with transition-metal ions (MnII, CoII), and alkaline earth ions (BaII), at different temperatures and at different pH values, resulting in the formation of five coordination polymers 1-5.
When the H4bmpb ligand was reacted with transition-metal ions (MnII, CoII), three coordination polymers were produced. Compounds 1 and 2 were prepared under different reaction conditions at different pH values. Compounds 1 and 2 were characterized by single-crystal X-ray diffraction analyses. The compounds are isostructures and adopt a 1D chain topology. Compound 3 was obtained as a co-crystal. The thermal stability and physical properties of the complexes were also examined.
Compounds 4 and 5 were produced by the reaction of H4bmpb with a transition-metal ion (CoII) in the presence of 4,4'-bipyridine or 2,2'-bipyridine. Compound 4 is a 2D coordination polymer. The 2D layers are further stacked into a 3D MOF. However, when the temperature was increased to 60 °C, compound 5 was produced. This compound is a 1D chain and the chains are further linked into a 2D sheet. The structures, thermal stabilities and physical properties of products 1-5 are discussed in this thesis.

並列關鍵字

coordination polymer ； phosphonate ligand ； self-assembly

參考文獻

[5](a) Mi, B. X.; Gao, Z. Q.; Liu, M. W.; Chan, K. Y.; Kwong, H. L.; Wong, N. B.; Lee, C. S.; Hung, L. S.; Lee, S. T. J. Mater. Chem. 2002, 12, 1307. (b) Itami, K.; Tonogaki, K.; Ohashi, Y.; Yoshida, J. Org. Lett. 2004, 6, 4093. (c) Liu, H.-J.; Tao, X.-T.; Yang, J.-X.; Yan, Y.-X.; Ren, Y.; Zhao, H.-P.; Xin, Q.; Yu, W.-T.; Jiang, M.-H. Crystal Growth & Design 2008, 8, 259.

[26]Wu, J.-Y.; Lin, Y.-F.; Chuang, C.-H.; Tseng, T.-W.; Wen, Y.-S.; Lu, K.-L. Inorg. Chem. 2008, 47, 10349.

[27]Miller, S. R.; Pearce, G. M.; Wright, P. A.; Bonino, F.; Chavan, S.; Bordiga, S.; Margiolaki, I.; Guillou, N.; Ferey, G. r.; Bourrelly, S.; Llewellyn, P. L. J. Am. Chem. Soc. 2008, 130, 15967.

[2]Hoskins, B. F.; Robson, R. J. Am. Chem. Soc. 1990, 112, 1546.

[8]Muller, P. Pure & Appl. Chem. 1994, 66, 1077.