臺灣博碩士論文加值系統

本研究中我們利用含有羧酸根與三氮六環吡啶基的配位子與鑭
系金屬的自組裝反應，得到一系列金屬有機骨架材料：
La2(BDC)3(DEF)4 (1)
Ln2(BDC)3(DEA)2 (2)
Ln(tptz)(BDC)Cl•DMA•H2O (3)
Ln2(tptz)2(BPDC)3(H2O)•3DMA•7H2O (4)
Ln2(1,4-pda)3(H2O)•2H2O (5)
Ln2(1,3-pda)3(H2O)3•H2O (6)
Dy4(1,3-pda)6(H2O)3(DMA)•2H2O (7)
Ln2(1,2-pda)3(H2O)2•2H2O (8)
X 光單晶繞射顯示化合物4 是一維結構，化合物3、6 和7 是二維結
構，化合物1、2、5 和8 是三維結構。
由吸脫附實驗與粉末繞射顯示，化合物5 和8 對水的吸附是可逆
的，將配位水與孔洞中的水脫去，仍然可維持其架構，Gd2(1,2-pda)3也對苯和二氯甲烷有不錯的吸附能力，每克化合物可吸附92 毫克的苯或33 毫克的二氯甲烷。由於鑭系金屬化合物具有獨特的放光性質，所以我們也針對所合成的這一系列的配位高分子之放光的性質作討論，發現苯二乙酸對Tb3+是一個很好的天線分子，我們預期這些化合物將是好的放光材料。

The novel metal-organic coordination polymers:
La2(BDC)3(DEF)4 (1)
Ln2(BDC)3(DEA)2 (2)
Ln(tptz)(BDC)Cl•DMA•H2O (3)
Ln2(tptz)2(BPDC)3(H2O)•3DMA•7H2O (4)
Ln2(1,4-pda)3(H2O)•2H2O (5)
Ln2(1,3-pda)3(H2O)3•H2O (6)
Dy4(1,3-pda)6(H2O)3(DMA)•2H2O (7)
Ln2(1,2-pda)3(H2O)2•2H2O (8)
have been synthesized and structurally characterized. Complex 4 is one-dimensional network. Complexes 3, 6 and 7 are two-dimensional frameworks, which are extended into three-dimensional network through π-π interactions or hydrogen bondings. Complexes 1, 2, 5 and 8 are three-dimensional frameworks.
TGA and XRPD prove that guest and coordinated water molecules in the framework of complexes 1 and 3 can be removed to generate permanent microporosity. The dehydration and rehydration processes were reversible. Gd2(1,2-pda)3 also have good capacity to absorb harmful
gases. Such as benzene(92mg/g) and dichloromethan (33mg/g). These coordination polymers of Tb3+ complexes exhibit Tb3+ characteristic emission in the range of 450-650 nm, and they could be anticipated as potential fluorescent materials.

一、前言 --------------------------------------------------------------------------1
二、實驗步驟--------------------------------------------------------------------9
2.1 實驗儀器-----------------------------------------------------------------9
2.2 藥品出處--------------------------------------------------------------- 10
2.3 合成步驟--------------------------------------------------------------- 11
三、X 光單晶繞射實驗及構造解析--------------------------------------- 17
四、結果與討論--------------------------------------------------------------- 75
4.1 La2(BDC)3(DEF)4(1) ------------------------------------------------ 75
4.2 Ln2(BDC)3(DEA)2(2) ----------------------------------------------- 79
4.3 Ln(tptz)(BDC)Cl•DMA•H2O(3) ------------------------------ 84
4.4 Ln2(tptz)2(BPDC)3(H2O)•3DMA•7H2O(4) ----------------- 92
4.5 Ln2(1,4-pda)3(H2O)•2H2O(5) ----------------------------------102
4.6 Ln2(1,3-pda)3(H2O)3•H2O(6) -----------------------------------114
4.7 Dy4(1,3-pda)6(H2O)3(DMA)• 2H2O(7) ------------------------125
4.8 Ln2(1,2-pda)3(H2O)2•2H2O(8) ----------------------------------133
五、結論-----------------------------------------------------------------------150
參考文獻-----------------------------------------------------------------------151
附圖 -----------------------------------------------------------------------------154
附表-----------------------------------------------------------------------------165

1. Long, J. R.; Yaghi, O. M. Chem. Soc. Rev. 2009, 38, 1213-1214.
2. James, S. L. Chem. Soc. Rev. 2003, 32, 276-288.
3. Freire, E.; Baggio, S.; Munoz, J. C.; Baggio; R. Acta Crystallogr., Sect. C 2002, 58, 221-224.
4. Charmant, J. P. H.; Jahan, A. H. M. M.; Norman, N. C.; Orpen, A. G.; Podesta, T. J. CrystEngComm. 2004, 6, 29-33.
5. Zhou, Y. F.; Jiang, F. L.; Xu, Y.; Cao, R.; Hong, M. C. J. Mol. Struct. 2004, 691, 191-195.
6. Zhang, Z. H.; Okamura, T.-a.; Zhu, H. F.; Sun, W. Y.; Ueyama, N.; Fan, J.; Liu, G. X.; Yu, K. B. Inorg. Chem. 2006, 45, 3941-3948.
7. Kitagawa, S.; Kitaura, R.; Noro, S-i. Chem. Int. Ed. 2004, 43, 2334-2375.
8. Britt, D.; Tranchemontagne, D.; Yaghi, O. M. Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 11623-11627.
9. Rowsell, J.; Millward, A.; Park, K. Yaghi, O. M. J. Am. Chem. Soc. 2004, 126, 5666-5667.
10. Kaye, S. S.; Dailly, A.; Long, J. R.; Yaghi, O. M. J. Am. Chem. Soc. 2007, 129, 14176-14177.
11. Bünzli, J. C.; Piguet, C. Chem. Soc. Rev. 2005, 34, 1048-1077.
12. Klink, S. I.; Grave, L.; Reinhoudt, D. N.; van Veggel, F. C. J. M. J. Phys. Chem. A 2000, 104, 5457-5468.
13. Reineke, T.; Eddaoudi, M.; Fehr, M.; Kelley, D.; Yaghi, O. M. J. Am. Chem. Soc. 1999, 121, 1651-1657. 152
14. Wang, Y. B.; Zhuang, W. J.; Jin, L. P.; Lu, S. Z. J. Mol. Struct. 2004, 705, 21-27.
15. Majumder, A.; Pilet, G.; Rodriguez, M. T. G.; Mitra, S. Polyhedron 2006, 25, 2550-2558.
16. El Fallah, M. S.; Majumder, A.; Mitra, S.; Ribas, J. Crystal Growth & Design 2006, 2355-2368.
17. Masuda, Y.; Wada, S.; Nakamura, T. Journal Alloys and compounds 2006, 1017-1021.
18. Berger, R. M.; Ellis, D. D., II. Inorg. Chim. Acta 1996, 241, 1-4.
19. Paul, P.; Tyagi, B.; Bhadbhade, M. M.; Suresh, E. J. Chem. Soc., Dalton Trans. 1997, 2273-2278.
20. Berger, R. M.; Holcombe, J. R. Inorg. Chim. Acta 1995, 232, 217-221.
21. Weng, D.; Zheng, X.; Li, L.; Yang, W.; Jin, L. J. Chem. Soc., Dalton Trans. 2007, 4822-4828.
22. Guo, X.; Zhu, G.; Fang, Q.; Xue, M.; Tian, G.; Sun, J.; Li, X.; Qiu, S. Inorg. Chem. 2005, 44, 3850-3855.
23. Yang, J.; Li, C.; Quan, Z.; Zhang, C.; Yang, P.; Li, Y.; Yu, C.; Lin, J. J. Phys. Chem. C 2008, 112, 12777-12785.
24. Yan, B.; Bai, Y.; Chen, Z. J. Mol. Struct. 2005, 741, 141-147.
25. de Bettencourt-Dias, A. Inorg. Chem. 2005, 44, 2734-2741.
26. Wan, Y.; Jin, L.; Wang, K.; Zhang, L.; Zheng, X.; Lu, S. New. J. Chem. 2002, 26, 1590-1596.
27. Guo, X.; Zhu, G.; Sun, F.; Li, Z.; Zhao, X.; Li, X.; Wang, H.; Qiu, S. Inorg. Chem. 2006, 45, 2581-2587. 153
28. Cui, G. H.; Li, J. R.; Zhang, R. H.; Bu, X. H. J. Mol. Struct. 2005, 740, 187-191.
29. Song, Y. S.; Yan, B.; Chen, Z. X. Can. J. Chem. 2004, 82, 1745-1751.
30. Pan, L.; Adams, K. M.; Hernandez, H. E.; Wang, X.; Zheng, C. ; Hattori, Y.; Kaneko, K. J. Am. Chem. Soc. 2003, 125, 3062-3067.
31. Zhou, Y. F.; Wang, R. H.; Wu, B. L.; Cao, R.; Hong, M. C. J. Mol. Struct. 2004, 697, 73-79.
32. Braverman, M. A.; LaDuca, R. L.; Crystal Growth & Design 2006, 2355-2368.