以1,10-二氮雜菲(1,10-phenanthroline)為基礎，所形成特殊類大環分子HDPA (bis(1,10-Phenanthrolin-2-yl)amine)的衍生物有別以往合成，L1。L1是與HDPA以往衍生物在不同氮上的取代，選擇其中一邊雜菲環上的外側氮加成而非在於橋雞氮上做取代，這樣的反應形成了一個不對稱的分子結構。而由於純化上替換陰離子所形成L2化合物。

    在L1以及L2的NMR光譜圖之間沒有太大差異，圖譜中由於不對稱性使得圖譜呈現許多個積分值為1的雙重峰，而且許多訊號峰有重疊情況難以判別因此利用二維的光譜技術，H-H COSY、HMQC及HMBC的方法來準確判別氫及碳的NMR光譜，並用ESI-MS確認其質量而確定是離子化合物以及有成功置換陰離子形成L2，並測量兩化合物的電化學性質。在酸鹼滴定實驗中，利用電子吸收光譜來偵測，經由計算後知道兩化合物的pKa值為3.31與2.98，並與起始物HDPA及橋基氮上取代衍生物做比較。並初步的測量兩化合物的電化學性質。

  這樣的結果是形成一個離子化合物，反應上有別於HDPA橋基氮上取代的簡易的反應程序以及最後的高產率。這樣的衍生物雖然與金屬上配位是不太可行的，但由於烷鏈末端是高反應性的碘，而有高反應性，在於衍生上還是有很大的可能。

In this research, new ionic compounds base on 1,10-phenanthroline, L1 and L2 were synthesized with high yield. L1 was synthesised by the reaction of macrocyclic molecule HDPA (bis(1,10-phenanthrolin-2-yl)amine) with 1,6-diiodohexane. The L1 was designed for different reaction site with HDPA derivatives synthesized in other research.
L1 is synthesized by the modification of phenanthroline instead of bridge nitrogen of HDPA and generate an asymmetric structure. L2 was synthesized by the exchange of anion for the solubility.
The H-H COSY, HMQC and HMBC technology were used for solving the aromatic signal of L1 and L2. And L1 and L2 were identified by ESI-MS. The acid titration UV-Vis  experiments shows Pka of L1 was 3.13 and Pka of L2 was 2.98. The oxidation potential of L1 were -0.19 eV, -0.89 eV and L2 were -0.73 eV, -1.07 eV. The reduction otenrial of L1 were 0.68 eV, 0.93 eV and L2 were 0.76 eV, 0.88 eV.

目錄

中文摘要
英文摘要

第一章  緒論                                                                   1
  1-1  環芳烴化合物                                                              1
  1-2  橋基雜菲分子                                                            2
  1-3  含氮橋基雜菲分子                                                        3
  1-4  設計                                                                    4

第二章  實驗                                                         5
  2-1  實驗藥品                                                                5
  2-2  實驗儀器                                                                6
     2-2-1  核磁共振光譜                                                       6
     2-2-2  電子吸收光譜儀                                                  6
     2-2-3  電灑法質譜分析儀                                               6
     2-2-4  電化學儀                                                      7
  2-3  酸滴定實驗                                                            7
  2-4  電化學實驗                                                            7
  2-5  合成                                                                  8
  
第三章  結果與討論                                                            14
  3-1  分子的合成                                                          14
     3-1-1  HDPA的合成                                                       15
     3-1-2  L1的合成                                                          15
     3-1-3  L2的合成                                                          15
  3-2  一般光譜圖                                                             17
     3-2-1  1H-NMR光譜圖                                                     17
     3-2-2  13C-NMR光譜圖                                                    20
     3-2-3  電灑離子化質譜                                                       21
     3-2-4  電子吸收光譜                                                        25
     3-2-5  循環伏安譜圖                                                         29
  3-3  二維核磁共振光譜圖                                                     31
     3-3-1  1H-1HCOSY                                                            31
     3-3-2  HMQC                                                            33
     3-3-3  HMBC                                                             35
  3-4  酸滴定                                                                 36
     3-4-1  L1酸滴定光譜                                                      37
     3-4-2  L2酸滴定光譜                                                      39
     3-4-3  酸解離常數計算                                                    41

第六章  結論                                                                  43

參考文獻                                                                      44

附錄                                                                          45
 
圖目錄

Figure 3-1 1H-NMR 300 MHz of L1 in DMSO-d6 .                                     18
Figure 3-2 1H-NMR 600 MHz of L1 in DMSO-d6 .                                     19
Figure 3-3 1H-NMR 300 MHz of L2 in DMSO-d6.                                     19
Figure 3-4 150 MHz 13C-NMR spectrum of the L1 in DMSO-d6 .                            20
Figure 3-5 ESI-MS spectrum of L1 ( c = 1 x 10-5 M) in CH3OH (full scan).                       21
Figure 3-6 ESI-MS spectrum of L1 ( c = 1 x 10-5 M) in CH3OH ,zoom scan for 584 m/z.            22
Figure 3-7 ESI-MS spectrum of L2 ( c = 1 x 10-5 M) in CH3OH                               23
Figure 3-8 ESI-MS spectrum of L2 ( c = 1 x 10-5 M)in CH3OH (zoom scan for 584 m/z )           23
Figure 3-9 ESI-MS spectrum of L2 ( c = 1 x 10-5 M) in CH3OH zoom scan for 292 m/z )           24
Figure 3-10 ESI-MS spectrum of L2 ( c = 1 x 10-5 M) in CH3OH for anion detection.( zoom scan for  
          PF6- m/z =145)                                                            24
Figure 3-11 ESI-MS spectrum of L2 ( c = 1 x 10-5 M) in CH3OH for anion detection.( zoom scan for I- 
           m/z =127)                                                               25
Figure 3-12 UV-vis spectrum of L1 in CH3CN in 298K , normailize abs. to 1.0 for wavelength           
           214nm.                                                                26
Figure 3-13 Variable-concentration UV-Vis spectra of L1 for different concentration.            26
Figure 3-14 Variable-concentration UV-Vis fitting spectra of L1 in CH3CN for different 
            concentration in 320 nm fitting. ( red line is fit linear of L1 )                       27
Figure 3-15 UV-vis spectrum of L2 in CH3CN in 298K, normailize abs. to1.0 for wavelength 
           214nm.                                                             28 
Figure 3-16 Uv-vis of PeDPA,HDPA L1and L2 normailize absorbance to1.0 for the highest peak in 
           210~250 nm.( all in CH3CN ).                                               29
Figure 3-17 Cyclic voltammograms of L1 in CH3CN solution at 298K.( 0.05M NBu4PF6 , Glassy 
           carbon electtode, 100m V/s scan rate)                                         30
Figure 3-18 Cyclic voltammograms of L2 in CH3CN solution at 298K.( 0.05M NBu4PF6 , Glassy 
           carbon electtode, 100m V/s scan rate)                                    31
Figure 3-19 600 MHz 1H-1H COSY spectrum of the L1 in DMSO-d6  ( for long alkyl chain).   32
Figure 3-20 600 MHz 1H-1H COSY spectrum of the L1 in DMSO-d6  ( for aromatic part ).   33
Figure 3-21 HMQC spectrum of the L1 in DMSO-d6.                                   34
Figure 3-22 HMQC spectrum of the L1 in DMSO-d6. ( for long alkyl chain )                34
Figure 3-23 HMQC spectrum of the L1 in DMSO-d6. ( for aromatic part )                   35
Figure 3-24 NMR 600 MHz HMBC spectrum of the L1 in DMSO-d6 (for aromatic part)        36
Figure 3-25 UV-vis absorption spectra pH acid titration of L1 ( c = 1.04 x 10-5 M ) in CH3CN drop 
          by HCl(aq) in CH3CN.                                                                          37
Figure 3-26 UV-vis absorption spectra pH acid titration of L1 ( 1.04 x 10-5 M in CH3CN ) as 
           function of pH between 6.85 and 4.40.                                       38
Figure 3-27 UV-vis absorption spectra pH acid titration of L1 ( 1.04 x 10-5 M in CH3CN ) as 
           function of pH between 4.40 and 2.26.                                       38
Figure 3-28 UV-vis absorption spectra pH acid titration of L2 (c = 3.23 x 10-5 M ) in CH3CN drop 
          by (c = 1.00x 10-2 M or 1.00 x 10-3 M ) HCl(aq) in CH3CN.                                   39
Figure 3-29 UV-vis absorption spectra pH acid titration of L2 ( 3.23 x 10-5 M in CH3CN ) as 
          function of pH between 6.70 and 4.13.                                    40
Figure 3-30 UV-vis absorption spectra pH acid titration of L2 ( 3.23 x 10-5 M in CH3CN ) as 
          function of pH between 4.13 and 1.87.                                    40
Figure 3-31 Variation of absorbance as s fouction of pH for L2 ( 3.23 x 10-5 M ) for slection of 
           wavelength. (point are the experimental point.)                                41
Figure 3-32 Plot of log [ ( Ai – A / A - Af ) ] vs. pH for wavelength 320 nm with L1 , 
          pKa = 3.13 ± 0.10 and Ka = 7.61 ( ± 1.73 ) x 10-4.                                         42
Figure 3-33 Plot of log [ ( Ai – A / A - Af ) ] vs. pH for wavelength 320 nm with L2,
          pKa = 2.98 ± 0.03 and Ka = 1.05 ( ± 0.5 ) x 10-3.                      43
Figure A-1 1H-NMR 300 MHz of L1 in DMSO-d6 .                                     46
Figure A-2 1H-NMR 300 MHz of L2 in DMSO-d6 .                                     47
Figure A-3 1H-NMR 600 MHz of L1 in DMSO-d6 .                                     48
Figure A-4 1H-NMR 600 MHz of L1 in DMSO-d6 (for long alkyl chain).                    49
Figure A-5 1H-NMR 600 MHz of L1 in DMSO-d6 (for aromatic part).                      50

表目錄

Scheme 1 Scheme 1 Synthesis of L1 and L2.                                        16
Scheme 2 Scheme 2 A reaction mechanism of CP reacted to HDPA.                            17
Table 5-1 Table of HDPA, NpDPA, L1 and L2 ( in CH3CN ) with pKa1 and pKa2 value.        43

參考文獻

1.	Gram, D. J.; Steinberg. H. J. Am. Chem. Soc. 1951, 73, 5691.
2.	Schubert, W. M.; Sweeny, W. A. and Latourette, H. K. ibid. 1954, 76, 5462.
3.	Cram, D. J.; Bauer, R. H. J. Am. Chem. Soc. 1959, 81, 5791
4.	Vriesema, B. K.; Buter, J. and Kellogg, R. M. J. Org. Chem. 1984, 49, 110-113
5.	Han, S.; Eltis, L. D.; Muchmore, S. W. Science 1995, 270, 976.
6.	Jiang, J.; Zhang, H.; Orf, G.S.; Lu, Y.; Xu, W.; Harrington, L.B.; Liu, H.; Lo, C. S.; Blankenship, R. E. Exp. Parasitology 2014, 1837,1904-1912 
7.	Shen, Y. and Sullivan, B. P. Inorg. Chem. 1995, 34, 6235-6236
8.	Nagaraj, K.; Velmurugan, G.; Sakthinathan, S.; Venuvanalingam, P. and Arunachalam, S. Dalton Trans. 2014, 43, 18074–18086
9.	Tinnemans, A. H. A.; Timer, K. ;Reinten, M.; Kraai jkamp, J. G.; Albers, A. H.; Linden, G. M.; Saaman, A. A. Inorg. Chem. 1981, 20, 3698-3703.
10.	Sigman, D. S. Biochemistry 1990, 29, 90097-9015.
11.	Youinou, M. T.; Ziessel, R.; Lehn, J. M. Inorg. Chem. 1991, 30, 2144-2148
12.	Marguerite. P.; Bruno. D.; Bernard. W. Inoorg. Chem. 1998, 37, 3486-3489
13.	Ogawa, S.; et al. Kogyo Kagaku Zasshi 1971, 83, 84-86
14.	蔡孟宏, 碩士論文, 私立淡江大學化學研究所, 民國102年6月
15.	高憲章, 博士論文, 私立淡江大學化學研究所, 民國99年5月
16.	Rook,Y.; Schmidtke,K.-U.; Gaube, F.; Schepmann, D.; Wunsch, B.; Heilmann, J.; Lehmann, J.; Winckler, T. J. Med. Chem. 2010, 53 (9), 3611–3617.
17.	許哲瑋, 碩士論文, 私立淡江大學化學研究所, 民國88年6月
18.	Bottger, M.; Wiegmann, B.; Schaumburg, S.; Jones, P. G.; Kowalsky, W. and Johannes, H. H. Beilstein J. Org. Chem. 2012, 8, 1037–1047.