本論文主要探討含嗒肼配位基與一價銅及二價鎳的金屬化合物化學。金屬鹽類Cu(CH3CN)4 ClO4 及 Ni(ClO4)2 • 6H2O 與配位子 C2-Me-(Clpdz)2 (L1) 、 C2-Me-(Ipdz)2 (L2) 、 C2-Me-(pdz-dmepzo)2 (L3) 反應，可得到四種金屬錯合物，其分子式如下: (Ni2L12) (ClO4)4 ， 1 ； (Cu5L33) (ClO4)5 ， 2 ； (Cu3L24) (ClO4)3 ， 3 ； (NiL1)(ClO4)2 ， 4 ，以上錯合物的晶體結構均已利用X-ray鑑定。

    錯合物 1 為雙核髮夾型錯合物，錯合物 2 與 3 均為螺旋結構，錯合物 4 為單核金屬錯合物。本論文中利用 Uv-vis 滴定來探討分子自我組裝的過程以及用螢光儀探討分子發光的機制。

A series of pyridazine ligands C2-Me-(Clpdz)2 (L1) 、 C2-Me-(Ipdz)2 (L2) 、 C2-Me-(pdz-dmepzo)2 (L3) and their copper ( I ) and nickel ( II )  complexes of the types  (Ni2L12) (ClO4)4 , 1 ； (Cu5L33) (ClO4)5 , 2 ； (Cu3L24) (ClO4)3 , 3 ； (NiL1)(ClO4)2 , 4 have been prepared. The complexes were produced by the reactions between ligands and Cu(CH3CN)4 ClO4 or Ni(ClO4)2 • 6H2O . All the complexes have been structurally characterized by X-ray crystallography.
    
    Complex 1 exhibits a hair-pin structure. Complexes 2 and 3 exhibits the helical structures . Complex 4 is a salt unit mononuclear Ni cation. The solution states of complexes and their self-assembling processes were examined by Uv-vis titration experiments to elucidate the reaction mechanism.

目錄
壹、緒 論.................................................................................................................................- 1 -
1.1 前言.............................................................................................................................- 1 -
1.1.1 超分子的發展...................................................................................................- 1 -
1.1.2 超分子的原理和特性......................................................................................- 1 -
1.1.3 超分子結合的驅動力......................................................................................- 2 -
1.1.4 超分子的應用..................................................................................................- 4 -
1.2 含金屬的無機超分子.................................................................................................- 5 -
1.3 螺旋超分子.................................................................................................................- 5 -
1.3.1 單股螺旋..........................................................................................................- 6 -
1.3.2 雙股螺旋..........................................................................................................- 7 -
1.3.3 三股螺旋..........................................................................................................- 7 -
1.3.4 四股螺旋..........................................................................................................- 8 -
1.4 螺旋錯合物的磁性.....................................................................................................- 9 -
1.5 實驗的策略與構想...................................................................................................- 11 -
1.5.1 配位子模型的概念........................................................................................- 11 -
1.5.2 鍵結區的設計................................................................................................- 12 -
1.5.3 連結區的設計................................................................................................- 13 -
1.6 研究目的...................................................................................................................- 14 -
貳、實 驗................................................................................................................................ 16 -
2.1 藥品...........................................................................................................................- 16 -
2.2 儀器...........................................................................................................................- 16 -
2.2.1 核磁共振儀 ( NMR )....................................................................................- 16 -
2.2.2 X-射線晶體結構解析 ( X-ray crystal structure analysis )........................- 16 -
2.2.3 電灑式質譜 ( ESI-Mass ).............................................................................- 16 -
2.2.4 電子吸收光譜 ( UV-Vis Spectrophotometer )............................................- 17 -
2.2.5 電子發光光譜 ( Luminescence Spectrometer ).........................................- 17 -
2.3 前驅物的合成...........................................................................................................- 17 -
2.3.1 3-(3,5-Dimethyl-pyrazol-1-yl)-6-hydrazino-pyridazine.............................- 17 -
2.3.2 3-Hydrazino-6-iodopyridazine. ( HzIpdz )..................................................- 18 -
2.3.3 3-Hydrazino-6-chloropyridazine. ( HzClpdz )............................................- 19 -
2.3.4 6,6’-Dibromo-4,4’-di(hexoxymethyl)-2,2’-bipyridine (Dbdhbpy).............- 20 -
2.3.5 Pyridazine-3,6-dialdehyde ( pdz-dia )..........................................................- 23 -
2.4 配位子的類型...........................................................................................................- 28 -
2.5 配位子的合成方法...................................................................................................- 32 -
2.6 錯合物的合成方法...................................................................................................- 34 -
第三章 結果與討論................................................................................................................- 36 -
3.1錯合物固態結構........................................................................................................- 36 -
3.1.1 Hair pin 錯合物.............................................................................................- 37 -
3.1.2 螺旋結構錯合物............................................................................................- 41 -
3.1.3 單核錯合物....................................................................................................- 49 -
3.2 吸收光譜與發光光譜的探討...................................................................................- 61 -
3.2.1 錯合物1 [Ni2L22](ClO4)4 L2=C2-Me-(Ipdz)2.............................................- 61 -
3.2.2 錯合物2 [Cu5L33](ClO4)5 L3=C2-Me-(pdz-dmepzo)2................................- 65 -
3.2.3 錯合物3 [Cu3L24](ClO4)3 L2=C2-Me-(Ipdz)2.............................................- 68 -
3.2.4 錯合物4 [NiL1](ClO4)2 L1=C2-Me-(Clpdz)2.............................................- 71 -
3.3 ESI-Mass 溶液態結構.............................................................................................- 75 -
3.3.1 錯合物1. [Ni2L2] (ClO4)4............................................................................- 75 -
3.3.2 錯合物 2. [Cu5L33](ClO4)5...........................................................................- 76 -
3.3.3 錯合物4. [NiL1(CH3CN)2] (ClO4)2..............................................................- 77 -
3.4 自組裝程序之研究方法...........................................................................................- 78 -
3.4.1 Ni(ClO4)2 對 L2 滴定探討 :........................................................................- 79 -
3.4.2 Ni(ClO4)2 對 L1 滴定探討 :........................................................................- 81 -
3.4.3 [Cu(CH3CN)2](ClO4) 對 L3 滴定探討 :....................................................- 82 -
3.4.4 [Cu(CH3CN)2](ClO4) 對 L2 滴定探討 :....................................................- 85 -
3.4.5 Ag(CF3SO3) 對 L4 滴定探討 :...................................................................- 86 -
3.5磁性探討....................................................................................................................- 98 -
3.5.1錯合物 1 磁性探討.......................................................................................- 99 -
肆、結 論..............................................................................................................................- 101 -
伍、參考文獻........................................................................................................................- 102 -

圖目錄
Figure 1-1 分子自組裝成超分子示意圖.................................................................................- 1 -
Figure 1-2 氫鍵複合體 ........................................................................................................- 2 -
Figure 1-3 氫鍵組裝的類型.....................................................................................................- 3 -
Figure 1-4 π-π堆疊的類型.....................................................................................................- 3 -
Figure 1-5 分子自我組裝型成的離子通道.............................................................................- 4 -
Figure 1-6 自我組裝與自我辨識的超分子.............................................................................- 5 -
Figure 1-7 螺旋錯合物的鍵結模式.........................................................................................- 6 -
Figure 1-8 多核單股螺旋錯合物.............................................................................................- 6 -
Figure 1-9 雙核雙股螺旋錯合物.............................................................................................- 7 -
Figure 1-10 雙核三股螺旋錯合物...........................................................................................- 8 -
Figure 1-11 四股螺旋錯合物的形式........................................................................................- 8 -
Figure 1-12 物質的磁性性質： a. 順磁 b. 鐵磁 c. 反鐵磁...............................................- 9 -
Figure 1-13 σ-π 路徑完成磁交換作用的螺旋錯合物...........................................................- 11 -
Figure 1-14 分子間π-π interaction磁偶作用的螺旋錯合物................................................- 11 -
Figure 1-15 配位子設計的概念.............................................................................................- 12 -
Figure 1-16 含N雜環的配位方式........................................................................................- 13 -
Figure 3-1 錯合物1的 ORTEP 圖.....................................................................................- 38 -
Figure 3-2 錯合物1中心鎳配位環境的 ORTEP 圖...........................................................- 38 -
Figure 3-3 錯合物1的 cylinder 圖......................................................................................- 39 -
Figure 3-4 錯合物1的 Space filling 圖...............................................................................- 39 -
Figure 3-5 錯合物1俯視圖...................................................................................................- 40 -
Figure 3-6 錯合物2 的 ORTEP 圖....................................................................................- 43 -
Figure 3-7 錯合物2 中心銅配位環境的 ORTEP 圖..........................................................- 43 -
Figure 3-8 錯合物2 的 cylinder 圖.....................................................................................- 44 -
Figure 3-9 錯合物2分子間的堆疊圖...................................................................................- 44 -
Figure 3-10 錯合物2分子內的π–π作用力..........................................................................- 45 -
Figure 3-11 錯合物2分子間的π–π作用力..........................................................................- 45 -
Figure 3-12 錯合物3 的 ORTEP 圖..................................................................................- 47 -
Figure 3-13 錯合物3中心銅配位環境的 ORTEP 圖.........................................................- 47 -
Figure 3-14 錯合物3分子內的 π–π 作用力......................................................................- 48 -
Figure 3-15 錯合物4 的 ORTEP 圖..................................................................................- 50 -
Figure 3-16 錯合物4 中心鎳配位環境的 ORTEP 圖........................................................- 50 -
Figure 3-17 錯合物4 的 ball and stick 圖...........................................................................- 51 -
Figure 3-18 錯合物4 分子間的 π–π 作用力.....................................................................- 51 -
Figure 3-19 配位子 L2 與錯合物 1 的吸收及發光光譜....................................................- 64 -
Figure 3-20 配位子 L3 與錯合物 2 的吸收及發光光譜....................................................- 67 -
Figure 3-21 配位子 L2 與錯合物 3 的吸收及發光光譜....................................................- 70 -
Figure 3-22 配位子 L1 與錯合物 4 的吸收及發光光譜....................................................- 73 -
Figure 3-23 [Ni2L22](ClO4)4 之ESI-Mass 圖譜.....................................................................- 75 -
Figure 3-24 [Cu5L33](ClO4)5 之 ESI-Mass 圖譜...................................................................- 76 -
Figure 3-25 [NiL1(CH3CN)2](ClO4)2 之 ESI-Mass 圖譜......................................................- 77 -
Figure 3-26 Ni2+ 金屬滴定L2 = C2-Me-(Ipdz)2......................................................................- 88 -
Figure 3-27 a. 滴定光譜的 EA plot ( Excess Absorbance Plot )........................................- 89 -
Figure 3-28 配位子L2 = C2-Me-(Ipdz)2 的質譜滴定............................................................- 91 -
Figure 3-29 質譜滴定的物種分佈圖.....................................................................................- 91 -
Figure 3-30 Ni2+ 金屬滴定L2 = C2-Me-(Clpdz)2................................................................- 92 -
Figure 3-31 a. 滴定光譜的EA plot ( Excess Absorbance Plot ).........................................- 93 -
Figure 3-32 Cu+ 金屬滴定L2 = C2-Me-(pdz-dmepzo)2.......................................................- 94 -
Figure 3-33 a. 滴定光譜的EA plot ( Excess Absorbance Plot ).........................................- 95 -
Figure 3-34 Cu+ 金屬滴定L3 = C2-Me-(Ipdz)2...................................................................- 96 -
Figure 3-35 滴定光譜的EA plot ( Excess Absorbance Plot )...............................................- 96 -
Figure 3-36 Ag+ 金屬滴定L = pdz-(Clpdz)2..........................................................................- 97 -
Figure 3-37 滴定光譜的EA plot ( Excess Absorbance Plot )...............................................- 97 -
Figure 3-38 [Ni2(L2)2](ClO4)4之(χmT)對溫度之作圖...........................................................- 100 -

表目錄
Table 2-1 Pyridazine-Dimethylpyrazole Arm........................................................................- 29 -
Table 2-2 Iodopyridazine Arm...............................................................................................- 30 -
Table 2-3 Chloropyridazine Arm...........................................................................................- 31 -
Table 3-1 錯合物1晶體數據與儀器參數.............................................................................- 52 -
Table 3-2 錯合物 1 的氫鍵表...............................................................................................- 53 -
Table 3-3 錯合物1重要的鍵長及鍵角列表.........................................................................- 53 -
Table 3-4 錯合物2晶體數據與儀器參數.............................................................................- 54 -
Table 3-5 錯合物 2 的氫鍵表...............................................................................................- 55 -
Table 3-6 錯合物2重要的鍵長及鍵角列表.........................................................................- 55 -
Table 3-7 錯合物3晶體數據與儀器參數.............................................................................- 57 -
Table 3-8 錯合物 3 的氫鍵表...............................................................................................- 58 -
Table 3-9 錯合物3重要的鍵長及鍵角列表.........................................................................- 58 -
Table 3-10 錯合物4的晶體資料...........................................................................................- 59 -
Table 3-11 錯合物 4 的氫鍵表.............................................................................................- 60 -
Table 3-12 錯合物4重要的鍵長及鍵角列表.......................................................................- 60 -
Table 3-13 所有配位子和錯合物的吸收光譜與發光光譜整理表.......................................- 74 -
Table 3-14 逐步生成常數與總生成常數表...........................................................................- 84 -
Table 3-15 計算所得的磁性參數.........................................................................................- 100 -

1   Lehn, J.-M. Supramolecular Chemistry; VCH: Weinheim, 1995.
2   Bianchi, A.; Bowman-James, K.; Garcia-Espana, E. Supramolecular Chemistry of Anions; John Wiley: New York, 1997.
3   Sauvage, J.-P. Transition Metals in Supramolecular Chemistry; John Wiley: New York, 1999.
4   Schneider, H.-J.; Yatsimirsky, A. Principles and Methods in Supramolecular Chemistry; John Wiley: New York, 2000.
5   Vögtle, F. Supramolecular Chemistry; John Wiley: New York, 1991.
6   Reinhoudt, D. N. Supramolecular Materials and Technologies; John Wiley: New York, 1999.
7   Lehn, J.-M. Science 1985, 227, 849–856.; 1993, 260, 1762–1763.
8   Kolotuchin, S.-V ; Zimmerman, S.-C; J. Am. Chem. Soc. 1998, 120, 9092-9093
9   Odriozola, I.; Kyritsakas, N.; Lehn, J.-M. Chem. Commun. 2004, 62–63.
10  Anderson, S.; Anderson, H. L.; Sanders, J. K. M. Acc. Chem. Revs. 1993, 26, 469–475.
11  (a) Ashton, P. R.; Ballardini, R.; Balzani, V.; Gandolfi, M. T.; Marquis, D. J.-F.;  
    Pérez-Garcia, L.; Prodi, L.; Stoddart, J. F.; Venturi, M. J. Chem. Soc., Chem. Commun. 
    1994, 177–180. (b) Ashton, P. R.; Stoddart, J. F.; Balzani, V.; Williams, D. J. J. Am. Chem. 
    Soc. 1995, 117, 11171–11197.
12  Amabilino, D. B.; Ashton, P. R.; Stoddart. J. F. Angew. Chem., Int. Ed. 1994, 33, 
    1286–1290.
13  Chiu, S.-H.; Pease, A. R.; Stoddart, J. F.; White, A. J. P.; Williams, D. J. Angew. Chem., Int. 
    Ed. 2002, 41, 270–274.
14  Barboiu, M.; Vaughan, G.; Kyritsakas, N.; Lehn J.-M. Chem. Eur. J. 2003, 9,   
    763-769
15  Constable, E. C. Chem. Ind.(London), 1994, 56–59.
16  Stadler, A.-M.; Kyritsakas, N.; Vaughan, G.; Lehn, J.-M. Chem. Eur. J. 2007, 13,   
    59-68
17  Petitjean, A.; Cuccia, L.-A.; Schmutz, M.; Lehn, J.-M. J. Org. Chem. 2008, 73, 
    2481-2495
18  Marquis, A.; Smith, V.; Harrowfield, J.; Lehn, J.-M.; Herschbach, H.; Sanvito,R.; 
    Emmanuelle, L.-W.; Dorsselaer, A.-V. Chem. Eur. J. 2006, 12, 5632-5641
19  Cahn, R. S.; Ingold, C.; Prelog, V. Angew. Chem., Int. Ed. 1966, 5, 385–415.
20  Meurer, K. P.; Vögtle, F. Top. Curr. Chem. 1985, 127, 1.
21  Zhou, X.-P.; Zheng, S.-L.; Zhang, X.; Wu, T. J. Inorg. Chem. 2006, 45, 
    7119-7125
22  Fletcher, N.-C.; Brown, R.-T.; Doherty, A.-P. J. Inorg. Chem. 2006, 45, 
    6132-6134
23  (a) Piguet, C.; Bünzli, J.-C. G.; Bernardinelli, G.; Hopfgartner, G.; Williams, A. 
    F. J. Am Chem. Soc. 1993, 115, 8197–8206. (b) Cotton, A. F.; Daniels, L. M.; 
    Jordan, G. T.; Murillo, C. A. J. Am. Chem. Soc. 1997, 119, 10377–10381. (c) 
    Chen, Y.-H.; Lee, C.-C.; Wang, C.-C.; Lee, G.-H.; Lai, S.-Y.; Li, F.-Y.; Mou, 
    C.-Y.; Peng, S.-M. Chem. Commun. 1999, 1667–1668.
24  (a) Chien, C.-H.; Chang, J.-C.; Yeh, C.-Y.; Lee, G.-H.; Fang, J.-M.; Peng, S.-M. 
    Dalton Trans. 2006, 2106–2113. (b) Ismayilov, R. H.; Wang, W.-Z.; Lee, G.-H.; 
    Peng, S.-M. Dalton Trans. 2006, 478–491. (c) Kuo, C.-K.; Chang, J.-C.; Yeh, 
    C.-Y.; Lee, G.-H.; Wang, C.-C.; Peng, S.-M. Dalton Trans. 2005, 3696–3701.
25  Kahn, O. Molecular Magnetism; VCH: Weinheim, 1993; Vol. 7-9, p 103-209.
26  Vázquez, M.; Bermejo, M. R.; Fondo, M.; Sorace, L. Eur. J. Inorg. Chem. 2001, 
1863-1868.
27  Vázquez, M.; Taglietti, A.; Gatteschi, D.; Sorace, L.; Sangregorio, C. J. Chem. 
Soc., Chem. Common. 1990, 621–622.
28  張清森, 淡江大學化研所博士論文
29  Price, J.-R.; Lan Y.; Jameson, G.-B.; Brooker, S. Dalton Trans., 2006, 1491-1494
30  Price, J.-R.; Lan, Y.; Brooker, S Dalton Trans., 2007, 1807-1820
31  Lan, Y.; Kennepohl, D.-K.; Moubaraki, B.; Murray, K.-S.; Cashion, J.-D.; Jameson, G.-B.; Brooker, S. Chem. Eur. J. 2004, 9, 3772-3784
32  湯上慰, 淡江大學化研所碩士論文
33  Steiner, G.; Gries, J.; Lenke, D. J. Med. Chem. 1981, 24, 59–63.
34  Amishiro, N.; Nagamura, S.; Kobayashi, E.; Gomi, K.; Saito, H. J. Med. Chem. 1999, 42, 
    669–676
35  Amb, C.-M.; Rasmussen, S.-C. J. Org. Chem, 2006, 71, 4696-4699
36  Tsukahara, Y.; Kamatani T.; Iino, A.; Suzuki, T.; Kaizaki, S. Inorg. Chem. 2002, 41, 4263-4370
37  Benedikt, L. -K.; Regis, G.; Joelle, S.; Charlot, M. -F.; Ally, A. Chem. Eur. J. 2008, 14, 4307-4317
38  Barbara, K.; Anna, K.; Krzysztof, K.; Julia, J.; Pawel, K. Polyhedron. 2000, 19, 2083-2093
39  Joe, B. G.; Brian, O. P.; Robert, M.; Robin, G. H. Inorg. Chem. 2008, 47, 1287-1294
40  Rojo, J.; Romero-Salguero, F. J.; Lehn, J.-M.; Baum, G.; Fenske, D. Eur. J. Inorg. Chem. 1999, 1421-1428.
41  Pfeil, A.; Lehn, J.-M. J. Chem. Soc., Chem. Commun. 1992, 838–840.
42  Zieesel, R.; Arriman, A.; Suffert, J.; Youinou, M.-T.; Cian, A.-D.; Fischer J. Angew. Chem., Int. Ed. 1997, 36, 2509–2511.
43  (a) Anderson, R. G. W. Cell Biology: A Comprehensive Treatise 4, Prescott D. M., Goldstein, L., Eds., Academic: New York, 1980, 393–441. (b) Marquis-Rigault, A.; Gervais, D. A.; Baxter, P. N. W.; Dorsselaer, A. V.; Lehn, J.-M. Inorg. Chem. 1996, 35, 2307–2310.q
44  Gampp, H.; Maeder, M.; Meyer, C. J. Talanta. 1985, 32, 95-101.
45  Gampp, H.; Maeder, M.; Meyer, C. J. Talanta. 1985, 32, 1133-1139.
46  Gampp, H.; Maeder, M.; Meyer, C. J. Talanta. 1986, 33, 943-951.
47  Constable, E. C.; Edwards, A. J.; Martinez-Manez, R.; Raithby, P. R. J. Chem. Soc. Dalton 
Trans. 1995, 3253-3261.
48  Carlin, R. L. Magnetochemistry; Springer-Verlag Berlin: Heidelberg, 1986.
49  Van Dnyneveldat, R. L.; Van Dnyneveldat, A. J.; Magnetic Properties of Transition Metel Compounds; Springer-Verlag: New York, 1997.
50  Figgis, B. N. Introduction to Ligand Theory; University of Weswern: Australia, 1962.
51  Mabbs, F. E.; Marchin, D. J. Magnetism and Transition Metal Complexes; Chapman and Hall: London, 1973.