臺灣博碩士論文加值系統

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。

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.

目錄
摘要 I
ABSTRACT II
致謝 IV
表目錄 VII
圖目錄 VIII
第一章 緒論 1
1.1. 前言 1
1.2. 配位聚合物 (COORDINATION POLYMER) 2
1.3. 實驗動機 21
第二章 實驗部分 25
2.1. 儀器與藥品 25
2.2. 有機配子與化合物合成 27
第三章 結果與討論 31
3.1. 化合物{[M(H2BMPB)(H2O)4]‧2H2O}N [M = CO (1), MN (2) ] 的合成與結構描述及其性質分析： 31
3.2. 化合物{[BA2(H2O)12‧(BMPB)]‧4H2O} (3)的合成與結構描述及其性質分析： 40
3.3. 化合物{[CO(H4BMPB)(4,4’-BPY)(H2O)2]‧2H2O}N (4)的合成與結構描述及其性質分析 44
3.4. 化合物{[CO(H4BMPB)(2,2’-BPY)(H2O)2]‧2H2O}N (5)的合成與結構描述及其性質分析 53
第四章 結論 60
參考資料 61
附錄 64

[1]http://diybio4beginners.blogspot.tw/2009/01/back-to-basics-reviewing-units-of.html
[2]Hoskins, B. F.; Robson, R. J. Am. Chem. Soc. 1990, 112, 1546.
[3](a) Llewellyn, P. L.; Bourrelly, S.; Serre, C.; Filinchuk, Y.; Ferey, G. Angew. Chem. Int. Ed. 2006, 45, 7751. (b) Mulfort, K. L.; Hupp, J. T. J. Am. Chem. Soc. 2007, 129, 9604. (c) Serre, C.; Mellot-Draznieks, C.; Surbls, S. N.; Ferey, G. Science 2007, 315, 1828. (d) Ma, S.; Yuan, D.; Chang, J. S.; Zhou, H. C. Inorg. Chem. 2009, 48, 5398. (e) Lin, X.; Telepeni, I.; Blake, A. J.; Dailly, A.; Brown, C. M.; Thomas, K. M.; Schroder, M. J. Am. Chem. Soc. 2009, 131, 2159.
[4](a) Jung, Y. J.; Kar, S.; Talapatra, S.; Soldano, C.; Viswanathan, G.; Li, X.; Yao, Z.; Ou, F. S.; Avadhanula, A.; Vajtai, R.; Curran, S.; Nalamasu, O.; Ajayan, P. M. Nano Lett. 2006, 6, 413. (b) Luechinger, N. A.; Loher, S.; Athanassiou, E. K.; Grass, R. N.; Stark, W. J. Langmuir 2007, 23, 3473.
[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.
[6]Furukawa, H.; Kim, J.; Ockwig, N. W.; O’Keeffe, M.; Yaghi, O. M. J. Am. Chem. Soc. 2008, 130, 11650.
[7]Banerjee, R.; Phan, A.; Wang, B.; Knobler, C.; Furukawa, H.; O’Keeffe, M.; Yaghi, O. M. Science 2008, 319, 939.
[8]Muller, P. Pure & Appl. Chem. 1994, 66, 1077.
[9]Roesky, H. W.; Andruh, M. Coord. Chem. Rev. 2003, 239, 91.
[10]Pielak, G. J.; Wang, X. Biochemistry, 2000, 40, 422.
[11]She, N.-F.; Gao, M.; Meng, X.-G.; Yang, G.-F.; Elemans, J. A. A. W.; Wu, A.-X.; Isaacs, L. J. Am. Chem. Soc. 2009, 131, 11695.
[12]Forster, P. M.; Burbank, A. R.; Livage, C.; Ferey, G.; Cheetham, A. K. Chem. Commun. 2004, 368.
[13]Long, L.-S. CrystEngComm 2010, 12, 1354.
[14]Withersby, M. A.; Blake, A. J.; Champness, N. R. Angew. Chem, Int Ed. 1997, 36, 2327.
[15]Deng, Z.-P.; Huo, L-H.; Qi, H.-L.; Zhu, L.-N.; Zhao, H.; Gao, S. Cryst Eng Comm 2010 , 12, 1354.
[16]Huang, X.-C.; Zhang, J.-P.; Chen, X.-M. J. Am. Chem. Soc. 2004, 126, 13218.
[17]Ma, B.-Q.; Coppens, P. Chem. Commun. 2003, 2290.
[18]Yang, M.; Jiang, F.; Chen, Q.; Zhou, Y.; Feng, R.; Xiong, K.; Hong, M. Cryst. Eng Comm, 2011, 13, 3971.
[19]http://www.labonline.com.au/articles/37723-Microwave-assisted-extraction
[20]Banerjee, R.; Furukawa, H.; Britt, D.; Knobler, C.; O’Keeffe, M.; Yaghi, O. M. J. Am. Chem. Soc. 2009, 131, 3875.
[21]Jiang, H.-L.; Liu, B.; Akita, T.; Haruta, M.; Sakurai, H.; Xu, Q. J. Am. Chem. Soc. 2009, 131, 11302.
[22]Li, Z.; Zhu, G.; Lu, G.; Qiu, S.; Yao, X. J. Am. Chem. Soc. 2010, 132, 1490.
[23]Soulier, B.; Lattuati-Derieux, A.; Thao, S.; Vaiedelich, S. Angew. Chem.，Int. Ed. 2010,49, 1.
[24](a) Konar, S.; Zon, J.; Prosvirin, A. V.; Dunbar, K. R.; Clearfield, A. Inorg. Chem. 2007, 46, 5229. (b) Fawcett, J.; Platt, A. W.G.; Vickers, S. Polyhedron. 2003, 22, 1431. (c) Stock, N.; Bein, T. J. Solid State Chem. 2002, 167, 330.
[25]Steel, P. J. Acc. Chem. Res. 2005, 38, 243.
[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.