臺灣博碩士論文加值系統

本論文研究主要為利用室溫自組裝反應，設計出過渡金屬與具有生物鹼基性質的有機配子反應形成之金屬－有機配位化合物。使用的有機配子：4,6-dihydroxypyrimidine (H2dhp)與2,4-dihydroxypyrimidine-5-carboxylic acid (H3dhpca)。將上述有機配子與鎳、鈣、錳、鎂與鋅等金屬離子以室溫自組裝方式，共合成得到五個金屬－有機配位化合物，有單體結構物 1, 3, 4, 5、二維結構物2等結構之產物。
依據有機配子的不同，區分為兩個部份加以說明:
第一部份：4,6-dihydroxypyrimidine (H2dhp)分別與鎳、鈣金屬鹽類反應，得到單核化合物[Ni(Hdhp)2(H2O)4] (1)與二維結構{[Ca(Hdhp)2(H2O)2]•THF}n (2)。
第二部份：2,4-dihydroxypyrimidine-5-carboxylic acid (H3dhpca)分別與錳、鎂和鋅金屬鹽類反應，合成出單核化合物[Mn(H2dhpca)2(H2O)2] (3)、單核化合物
{[Mg(H2dhpca)2(H2O)2]•2H2O} (4)與單核化合物{[K2(H2O)6][Zn(H2dhpca)2(H2O)2]} (5)。
產物經由單晶X射線繞射解析得到晶體結構，並利用IR，以及TGA、粉末 X射線繞射解析鑑定，測定其性質。

This thesis focuses on the preparation of based metal–organic frameworks based on nucleobases via a self-assembly strategy. Two uracil-derivatives, 4,6-dihydroxypyrimidine (H2dhp) and 2,4-dihydroxypyrimidine-5-carboxylic acid (H3dhpca), were selected for use as potential organic ligands. The assembly of CaII, NiII ions with 4,6-dihydroxypyrimidine (H2dhp) in water or alcohol at ambient temperature led to the formation of the discrete molecule [Ni(Hdhp)2(H2O)4] (1) and a 2D metal–organic frameworks {[Ca(Hdhp)2(H2O2)]•THF}n (2). When MnII, MgII and ZnII were reacted with 2,4-dihydroxypyrimidine-5-carboxylic acid (H3dhpca) in water or alcohol at ambient temperature, the discrete compounds [Mn(H2dhpca)2(H2O)2] (3), {[Mg(H2-dhpca)2(H2O)2]•2H2O} (4) , and {[K2(H2O)6][Zn(H2dhpca)2(H2O)2]} (5) were produced.
The solid-state structures of the products were characterized by single-crystal X-ray diffraction analyses and their thermal stabilities were examined by TGA method.

摘要 i
ABSTRACT ii
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
第一章 緒論 1
1.1 前言 1
1.2 超分子化學 (Supramolecular Chemistry) 2
1.3 配位聚合物 (Coordination Polymer) 8
1.4 孔洞性配位聚合物 (Porous Coordination Polymers) 15
1.5 實驗動機 21
第二章 實驗部分 28
2.1 儀器與藥品 28
2.2 金屬–有機配位聚合物之合成 30
2.2.1第一部分:4,6-dihydroxypyrimidine(H2dhp)與金屬鹽類之合成 30
2.2.2第二部分:2,4-dihydroxypyrimidine-5-carboxylic acid(H3dhpca)與金屬鹽類之合成 34

第三章 結果與討論 40
3.1第一部分:4,6-dihydroxypyrimidine(H2dhp)與金屬鹽類 40
3.1.1化合物[Ni(H-dhp)2(H2O)4] (1)的合成與結構描述及其性質分析 40
3.1.2化合物{[Ca(H-dhp)2(H2O)] •H2O•THF}n (2)的合成與結構描述及其性質分析 50
3.2第二部分:2,4-dihydroxypyrimidine-5-carboxylic acid(H3dhpca)與金屬鹽類 62
3.2.1化合物[Mn(H2-dhpca)2(H2O)2] (3)的合成與結構描述及其性質分析 62
3.2.2化合物{[Mg(H2-dhpca)2(H2O)2]•H2O} (4)的合成與結構及其性質分析 71
3.2.3化合物{[K2(H2O)6][Zn(H2dhpca)2(H2O)2]} (5)的合成與結構描述及其性質分析 81
3.3化合物1~5探討 90
第四章 結論 94
參考資料 95
附錄............. 99
附圖....... 123

[1](a) Ockwig, N. W.; O''Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2005, 38, 176?185.(b) Mynar, J. L.; Lowery, T. J.; Wemmer, D. E.; Pines, A.; Fréchet, J. M. J. Am. Chem. Soc. 2006, 128, 6334?6335. (c) Sugimoto, T.; Suzuki, T.; Shinkai, S.; Sada, K. J. Am. Chem. Soc. 2007, 129, 270?271. (d) O''Keeffe, M.; Yaghi, O. M. Angew. Chem. Int. Ed. 2008, 47, 5136?5147. (e) Tranchemontagne, D. J.; Mendoza?Cortés, J.; O'' Keeffe, M.; Yaghi, O. M. Chem. Soc. Rev. 2009, 38, 1257?1283.
[2](a) Llewellyn, P. L.; Bourrelly, S.; Serre, C.; Filinchuk, Y.; Férey, G. Angew. Chem. Int. Ed. 2006, 45, 7751?7754. (b) Mulfort, K. L.; Hupp, J. T. J. Am. Chem. Soc.2007, 129, 9604?9605. (c) Serre, C.; Mellot-Draznieks, C.; Surbls, S. N.; Férey, G. Science 2007, 315, 1828?1831. (d) Ma, S.; Yuan, D.; Chang, J. S.; Zhou, H. C. Inorg. Chem. 2009, 48, 5398?5402. (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?2171.
[3](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. NanoLett. 2006, 6, 413?418. (b) Luechinger, N. A.; Loher, S.; Athanassiou, E. K.; Grass, R. N.; Stark, W. J. Langmuir 2007, 23, 3473?3477.
[4](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?1311. (b) Itami, K.; Tonogaki, K.; Ohashi, Y.; Yoshida, J. Org. Lett. 2004, 6, 4093?4096. (c) Liu, H. J.; Tao, X. T.; Yang, J. X.; Yan, Y. X.; Ren, Yan.; Zhao, H. P. Cryst. Growth Des. 2008, 8, 259?264.
[5](a) Manson, J. L.; Lee, C.; Whangbo, M. H. Chem. Mater. 2008, 20, 7408?7416. (b)Mondal, K. C.; Mukherjee, P. S. Inorg. Chem. 2008, 47, 4215?4225. (c) Zheng, Y.Z.; Chen, X. M.; Long, G. J. Inorg. Chem. 2009, 48, 2028?2042.
[6](a) Laine, H.; Li, A.; O''Keeffe, M.; Yaghi, O. M. Science 1999, 283, 1145?1147. (b) Zheng, N. X.; Feng, B. P. J. Am. Chem. Soc. 2003, 125, 1138?1139. (c) Prakash, M. J.; Radhakrishnan, T. P. Chem. Mater. 2006, 18, 2943?2949.
[7]Lehn, J. M. Pure Appl. Chem. 1978, 50, 871.
[8]Schneider, H.J.; Yatsimirsky, A.; “Principles and Methods in Supramolecular Chemistry”, John Wiley & Sons Ltd, 2000.
[9]Sauvage, J. P.; “Transition Metals in Supramolecular Chemistry”, John Wiley & Sons Ltd, 1999.
[10]Lehn, J.-M., Science 1985, 227, 849.
[11]Lehn, J. M. Nobel lecture 1987, 444?491.
[12]Prins, L. J.; Reinhoudt, D. N.; Timmerman, P. Angew. Chem. Int. Ed. 2001, 40, 2382.
[13]Schmuck, C.;Wienand, W. Angew. Chem. Int. Ed. 2001, 40, 4363.
[14]Ma, Y.; Kolotuchin, S. V.; Zimmerman, S. C. J. Am.Chem. Soc. 2002, 124, 13757.
[15]Lehn, J. M., Angew. Chem. Int. Ed. Engl. 1993, 32, 69.
[16]Uppadine, L. H.; Lehn, J.-M.; Angew. Chem. Int. Ed. 2004, 43, 240.
[17]Yi, L.; Yang, X.; Lu, T.; Cheng, P.Cryst Growth & Des. 2005,5, 1215
[18]Steel, P. J.; Sumby, C. J.; Chem. Commun. 2002, 322.
[19]Saalfrank, R. W.; Glaser, H.; Demleitner, B.; Hampel, F.;Chowdhry, M. M.; Schunemann, V.; rautwein, A. X.;Vaughan, G. B. M.; Yeh, R.; Davis, A. V.; Raymond, K.N.; Chem. Eur. J. 2002, 8, 493.
[20]Steed, J.W. ; Atwood, J.W. supramolecular chemistry 2006, 5, 15-21
[21]Berg, J. M.; Tymoczko, J. L.; Stryer, L. Biochemistry, W. H. Freeman and Company, New York 2001, 425?464.
[22]Steed, J.W. ; Atwood, J.W. supramolecular chemistry 2006, 5, 15?21
[23]Roesky, H. W.; Andruh, M. Coord. Chem. Rev.2003, 239, 91?119.
[24]Christoph, J. J. Chem. Soc., Dalton. Trans.2000, 21, 3885?3896.
[25]Avalos, M.; Babiano, B.; Cintas, P.; Jimenez, J. L.; Palacios, J. C. Chem. Commun.2003, 887.
[26]Chen, B.; Ockwig, N. W.; Millward, A. R.; Contreras, D. S.; Yaghi, O. M. Angew. Chem., Int. Ed. Engl. 2005, 44, 4745.
[27]Kitagawa, S.; Kitaura, R.; Noro, S.-I. Angew. Chem., Int. Ed. 2004, 43, 2334.
[28]Zaworotko, M. J. Chem. Commun.2001, 1, 1.
[29]Moulton,B.; Zaworotko, M. J. Chem. Rev. 2001, 101, 1629?1658.
[30]Ouellette, W.; Prosvirin, A. V.; Chieffo, V.; Dunbar, K. R.; Hudson, B.; Zubieta, J. Inorg. Chem.2006,45,9346.
[31]Raberau, A. Angew. Chem., Int. Ed. Engl.1985, 24, 1026.
[32]Fajita, M.; Kwon, Y. J.; Washizu, S.; Ogura, K. J. Am. Chem. Soc.1994, 116, 1151.
[33]Kitagawa, S.; Uemura, K. Chem.Soc. Rev. 2005, 34, 109.
[34]Kitagawa, S.; Kitaura, R.; Noro, S.-I. Angew. Chem., Int. Ed.2004, 43, 2334.
[35]Siegbahn, K. Pure &Appl. Chem.1976, 46, 77.
[36]Ying, J. Y.; Mehnert, C. P.; Wong, M. S. Angew. Chem. Int. Ed.1999, 38, 56?77.
[37](a)Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O''Keeffe, M.; Yaghi, O. M. Science2002, 295, 469?472. (b) Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D.; Kim, J.; O''Keeffe, M.; Yaghi, O. M. Science2003, 300, 1127?1129.
[38](a) Banerjee, R.; Phan, A.; Wang, B.; Knobler, C.; Furukawa, H.; O''Keeffe, M.;
Yaghi, O. M. Science2008, 319, 939?943. (b) Wang, B.; Furukawa, H.; O''Keeffe, M.; Yaghi, O. M. Nature2008, 453, 207?212
[39] Furukawa, H.; Kim, J.; Ockwig, N. W.; O''Keeffe, M.; Yaghi, O. M. J. Am. Chem. Soc.2008, 130, 11650?11661.
[40] 陳惠芳,中國文化大學碩士論文 2007