銅、鋅、鎘金屬離子與含 Tetrazole 配子之自組裝合成、性質鑑定之研究

Design of Inorganic-Organic Hybrid Materials Based on Tetrazole Ligands

廖光駿(Kuang-Jun Liao)

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(2007年)

https://doi.org/10.6841/NTUT.2007.00119

摘要

本論文探討含tetrazole配子4-(1H-tetrazo-5-yl)benzoic acid、5-pyrazinetetrazole 與銅、鋅及鎘離子之室溫或水熱自組裝反應，並研究生成的配位聚合物結構與各項性質。 以有機配子 4-(1H-tetrazo-5-yl)benzoic acid 和硝酸鋅以水熱法反應，得到三維配位聚合物 [Zn2(C8H4N4O2)2]n (1)；若和硝酸鎘以室溫自組裝或水熱法反應，可得到三維配位聚合物 [Cd(C8H4N4O2)(H2O)]n (2)。 以5-pyrazinetetrazole 與鎘金屬離子以水熱法合成反應，可得到二維配位聚合物 [Cd3(C5H3N6)2Cl4(H2O)2]n (3) 及錯合物[Cd(C5H3N6)2(H2O)2] (4)；若和銅、鋅金屬離子以水熱法反應，分別得到錯合物[Cu(C5H3N6)2(H2O)2]•H2O (5)、[Zn(C5H3N6)2(H2O)2] (6)。 本論文中共合成得六個新型含金屬－有機的配位化合物，其結構經IR、UV-Visible等光譜分析，以及單晶、粉末X射線繞射解析鑑定，並利用TGA測定其熱安定性質。

關鍵字

自組裝 ； 超分子 ； 配位化合物

並列摘要

The aim of this study was to develop a self-assembly strategy for the preparation of metal-organic supramolecules and coordination polymers.
Reaction of Zn(NO3)2•6H2O with 4-(1H-tetrazo-5-yl)benzoic acid under hydrothermal conditions produced a 3D polymer [Zn2(C8H4N4O2)2]n (1). Treatment of Cd(NO3)2•4H2O with 4-(1H-tetrazo-5-yl)benzoic acid at ambient temperature or under hydrothermal conditions yielded a 3D polymer [Cd(C8H4N4O2)(H2O)]n (2).
The reaction of CdCl2•2.5H2O with 5-pyrazinetetrazole under hydrothermal conditions produced a 2D polymer [Cd3(C5H3N6)2Cl4(H2O)2]n (3), and a discrete molecule [Cd(C5H3N6)2(H2O)2] (4).
In contrast, the reaction of 5-pyrazinetetrazole with CuCl2•2H2O or Zn(NO3)2•6H2O under hydrothermal conditions led to the formation of discrete molecules [Cu(C5H3N6)2(H2O)2]•H2O (5) and [Zn(C5H3N6)2(H2O)2] (6), respectively.
Compounds 1-6 were characterized with the aid of elemental analysis, IR, and UV-visible spectroscopic studies, thermal analysis (TGA) and X-ray powder diffraction studies. The molecular structures of the products 1-6 were determined by single-crystal X-ray diffraction analysis.

並列關鍵字

Self-assembly ； supramolecule ； coordination polymer ； tetrazole

參考文獻

(5) (a) Gregory, J. K.; Clary, D. C. J. Phys. Chem. 1996, 100, 18014. (b) Ugalde, J. M.; Alkorta, I.; Elguero, J. Angew. Chem. Int. Ed. 2000, 39, 717. (c) Ghosh, S. K.; Bharadwaj, P. K. Inorg. Chem. 2003, 42, 8250. (d) Liu, Y. H.; Lu, Y. L.; Wu, H. C.; Wang, J. C.; Lu, K. L. Inorg. Chem. 2002, 41, 2592-2597.

(6) Luo, T. T.; Tsai, H. L.; Yang, S. L.; Liu, Y. H.; Yadav, D. R.; Su, C. C.; Ueng, C. H.; Lin, L. G.; Lu, K. L. Angew. Chem., Int. Ed. 2005, 44, 6063-6067.

(10) (a) Stassen, A. F.; Grunert, M.; Mills, A. M.; Spek, A. L.; Haasnoot, J. G.; Reedijk, J.; Linert, W. Dalton 2003, 3628-3633. (b) Tao, J.; Ma, Z.-J.; Huang, R.-B.; Zheng, L.-S. Inorg. Chem. 2004, 43, 6133-6135. (c) Jiang, C.; Yu, Z.; Wang, S.; Jiao, C.; Li, J.; Wang, Z.; Cui, Y. Eur. J. Inorg. Chem. 2004, 18 3662-3667. (d) Wang, X. S.; Tang, Y. Z.; Huang, X. F.; Qu, Z. R.; Che, C. M.; Chan, P. W. H.; Xiong, R. G. Inorg. Chem. 2005, 44, 5278-5285.

(12) Chen, B.; Ockwig, N. W.; Millard, A. R.; Contreras, D. S.; Yaghi, O. M. Angew. Chem. 2005, 117, 4823; Angew. Chem. Int. Ed. 2005, 44, 4745.

(1) Ye, B. H.; Ding, B. B.; Weng, Y. Q.; Chen, X. M. Inorg. Chem. 2004, 43, 6866.