使用氯化亞鐵和經由三氟醋酸酸化過的[H4HAPP(TFA)2]進行反應，經過清洗後，再利用甲醛與產物進行加熱迴流，使其溶解度增加，再利用過量HCl 合成出[Fe(H2HAPP)Cl2]Cl，由電灑質譜發現在
含水溶劑中，有雙核錯合物的產生，在利用元素分析、電子吸收光
譜、氫核磁共振光譜，可以判定[Fe(H2HAPP)Cl2]Cl 單核錯合物在含水溶液中確實可以自氧化形成μ-oxo dimer 雙核鐵錯合物，而由於μ-oxo dimer 雙核鐵錯合物在水溶液中還具有氧化的現象，由電子吸收光譜從655nm 吸收峰紅位移至830 nm 吸收峰，以及氫核磁共振光譜所表示的積分值剛好為1:2，此現象讓我們由原本推測μ-oxo
dimer 雙核鐵錯合物氧化態的改變所造成紅位移現象，而開始大膽假設μ-oxo dimer 雙核鐵錯合物，在水溶液中也可以自身氧化形成三核錯合物的可能，由其在加熱及添加氧化劑的電子吸收光譜，皆可以促進三核錯合物加速升成，也利用透光薄層電極( OTTLE )，來加以氧化水溶液中的錯合物，也可以發現同樣的結果。
有了此推測，我們也對水溶液中進行錯合物的性質研究，由於H2HAPP 橋基氮上可以接受或提供質子，因此對電子吸收光譜酸鹼
滴定可得到pKa=4.07，也利用pyridine 及imidazole 來進行軸向配位置換，也經由電灑質譜及電子吸收光譜證實之。

In this research, [Fe(H2HAPP)Cl2]Cl had been synthesized by acidified the ligand [H4HAPP(TFA)2] by TFA and reacted with FeCl2. The product were refluxed with formaldehyde to increase the solubility and recrystalized by add excess HCl.
[Fe(H2HAPP)Cl2]Cl were characterized by EA, ESI-MS, NMR. The ESI-MS result revealed that the complex were able to form the dimmer form in water-contained solvent. The coupling processes were proofed by temperature-varition NMR and absorption spectra. The NMR spectrum of [Fe(H2HAPP)Cl2]Cl in D2O showed broad peaks at 3.99 ppm(b)、6.55 ppm(b)、10.87 ppm(b) and sharp peaks at 7.10 ppm (d) 、
7.15 ppm (d)、7.82 ppm (s)、7.89 ppm (s)、8.46 ppm (d)、8.58 ppm (d) implied the trimer form of complexes. This hypothesis were researched by redox absorption spectra and OTTLE spectroscopy technique.
The property of the complex in water has researched. The absorption spectrum of acid / base titrate the trimer complex shows pKa=4.07, due to the bridged N of H2HAPP can be proton receptor and donor. Utilize pyridine and imidazole to possess axial replacement, which also can be confirmed by ESI-MS and absorption spectrum.

第一章 緒論 ………………………………………………………..1
第二章 實驗……………………………………………………………8
2.1 試劑……………………………………………………………….8
2.2 H2HAPP 合成……………………………………………………..9
2.3 鐵錯合物的合成…………………………………………………14
2.4 物理鑑定…………………………………………………………17
第三章 結果與討論………………………………………………...19
3.1 [Fe(H2HAPP)Cl2]Cl 鐵錯合物的合成……………………....19
3.1.1 配位子H2HAPP 的合成…………………………………….19
3.1.2 [Fe(H2HAPP)Cl2]Cl 鐵錯合物的合成…………………....19
3.2 [Fe(H2HAPP)Cl2]Cl 鐵錯合物的成分鑑定…………………….20
3.3 [Fe(H2HAPP)Cl2]Cl 鐵錯合物水溶液中的變化……………..23
3.4 [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP))]
鐵錯合物化學性質研究………………………………………………35
3.4.1 電子吸收光譜氧化還原滴定…………………………………35
3.4.2 電子吸收光譜酸鹼滴定………………………………………41
3.4.3 電子吸收光譜軸向配位滴定…………………………………45
3.4.4 循環伏安法( CV )…………………………………………..49
3.4.5 透光薄層電化學法( OTTLE )…………………………………52
第四章 結論……………………………………………………………55
第五章 參考文獻………………………………………………………56
第六章 附錄……………………………………………………………60
流程目錄
Scheme 1.1 Synthesis of H2HAPP by Ogawa………………………5
Scheme 1.2 Synthesis of H2HAPP by our lab..……………….6
Scheme 2.1 Synthesis of Hexaaza-1,10-phenanthrolinocyclophane. ...............................9
Scheme 3.1 Synthesis of monomer complex. ………………….20
Scheme 3.2 [Fe(H2HAPP)Cl2]Cl in H2O. …………………………35
Scheme 3.3 Protonation of [Fe(H2HAPP)Cl2]Cl in H2O………44
表目錄
Table 3.1 Elemental analysis list of [Fe(H2HAPP)Cl2]Cl. ( Sulfanilic acid as Standard )...........................20
Table 3.2 Peak list of [Fe(H2HAPP)Cl2]Cl in ESI-MS spectra of Figure 3.2 ( in MeOH )……………………………………….23
Table 3.3. Peak list of [Fe(H2HAPP)Cl2]Cl in ESI-MS spectra of Figure 3.3 (in MeOH:H2O=8:2 )……………………24
Table 3.4 Peak list of [Fe(H2HAPP)Cl2]Cl in ESI-MS spectra of Figure 3.22 ( in 10% HCl )………………………………..45
Table 3.5 Peak list of of [(Fe(HAPP))3O2] in H2O and 10% pyridine ………...…....................................49
Table 3.6 Peak list of of [(Fe(HAPP))3O2] in H2O and 10% imidazole ……………....................................49
圖目錄
Figure 1.1 Porphyrin and Porphyrinogen………………........1
Figure 1.2 Tetraphenylporphyrin and Tetra(p-methylphenyl)porphyrin…………….......................................1
Figure 1.3 Octaethylporphyrin and Tetrabenzoporphyrin……2
Figure 1.4 S2TTP and N-confused porphyrin……………………2
Figure 1.5 Sapphyrin and Corrole……………………………...2
Figure 1.6 Catalytic Cycle of Cytochrome P450………………3
Figure 1.7 Oxygen binding…………………………………………4
Figure 3.1 UV-Vis spectra of [Fe(H2HAPP)Cl2]Cl in MeOH…21
Figure 3.2 ESI-MS of [Fe(H2HAPP)Cl2]Cl in MeOH ……………22
Figure 3.3 ESI-MS of [Fe(H2HAPP)Cl2]Cl in MeOH：H2O＝8：2…………................................................24
Figure 3.4 UV-Vis spectra of [Fe(H2HAPP)Cl2]Cl in H2O……26
Figure 3.5 UV-Vis spectra of Fe(H2HAPP)Cl2]Cl in H2O; Solid line is observed by fresh prepare, Dash line is observed after 2 hr, Dot line is observed after 2
day. ………………………………………………………….……..27
Figure 3.6 Change with time in the UV-Vis spectra of [Fe(H2HAPP)Cl2]Cl in H2O
( 50℃ )………………………………....………………………..27
Figure 3.7 1H-NMR spectrum of [(Fe(H2HAPP)Cl2]Cl in D2O at 300K………..............................................30
Figure 3.8 Change with temperature in the NMR spectrum of [Fe(H2HAPP)Cl2]Cl in D2O…….............................32
Figure 3.9. 1H-NMR spectrum of [(Fe(H2HAPP)Cl2]Cl in D2O at 300K (after heat)..…………………………………….....33
Figure 3.10 Raman of [Fe(H2HAPP)Cl2]Cl in H2O …………….34
Figure 3.11. UV/Vis spectrum of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)] in H2O...…………………………………………….…..36
Figure 3.12 UV-Vis spectra changes observed upon addition Ascorbic acid to aqueous solution of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)].…..…………............................……36
Figure 3.13 UV-Vis spectra changes observed upon addition Ascorbic acid to aqueous solution of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)]……………..…...............................37
Figure 3.14 UV-Vis spectra changes observed upon addition Ascorbic acid to aqueous solution of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)]…………………...............................37
Figure 3.15 UV-Vis spectra changes observed upon addition Na2S2O8 to aqueous solution of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)]………………......................................38
Figure 3.16 UV-Vis spectra changes observed upon addition Na2S2O8 to aqueous solution of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)]....…………..................................…..38
Figure 3.17 UV-Vis spectrum changes observed upon addition Na2S2O8 to aqueous solution of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)]…………...….....................................39
Figure 3.18 UV-Vis spectrum changes observed upon addition Na2S2O8 to aqueous solution of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)]…………...….....................................40
Figure 3.19 UV-Vis spectra taken during a titration of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)] aqueous solution by HCl(aq)；pH range from 5.55 to 1.38..…………………………………….41
Figure 3.20 UV-Vis spectra taken during a titration of [Fe(HAPP)(O)Fe(HAPP)(O) Fe(HAPP)] aqueous solution by HCl(aq)；pH range from 1.85 to 3.11....…………………...…..42
Figure 3.21 Plot of log[(Ai-A)/(A-Af)] vs. pH (412nm)；Change with pH in the UV-Vis spectra (pH 5.5~1.38) ……..43
Figure 3.22 ESI-MS of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)] in 10% HCl..………………………………………………………………44
Figure 3.23 UV-Vis spectra taken during a titration of [Fe(HAPP)(O)Fe(HAPP) (O)Fe(HAPP)] aqueous solution by imidazole…………….............................…….……46
Figure 3.24 UV-Vis spectra taken during a titration of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)] aqueous solution by pyridine……………...........................…….……...46
Figure 3.25 ESI-MS of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)] in H2O and 10%pyridine……...……………………………………….47
Figure 3.26 ESI-MS of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)] in H2O and 10% imidazole.................……………………….48
Figure 3.27 Cyclic voltammogram of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)] in 0.01M NH4PF6 / H2O under nitrogen ; scan rate:100mV/s ; Glassy carbon electrode ; counter electrode, Pt rod………………............….……………….51
Figure 3.28 Optically transparent thin-layer electrode……………………………..........................52
Figure 3.29 UV-Vis absorption spectra of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)] in aqueous solution + 0.1M KCl on a Pt OTTLE with apply voltage 500mV to 160mV………………………52
Figure 3.30 UV-Vis absorption spectra of [Fe(HAPP)(O)Fe(HAPP)(O)Fe(HAPP)] in aqueous solution + 0.1M KCl on a Pt OTTLE with apply voltage 160 mV to -100 mV…...…………..53
Figure 3.31 Plot of Absorbance vs. E(V)..………………...54
Figure 3.32 UV-Vis spectra of [Fe(H2HAPP)Cl2]Cl in different ratio of MeOH and H2O..………………………………28
附圖目錄
附圖一. EA of [Fe(H2HAPP)Cl2]Cl…………………………………60
附圖二. IR of [Fe(H2HAPP)Cl2]Cl ………………………………61
附圖三. 1H-NMR spectrum of H2HAPP in CF3COOD at 298K ……62
附圖四. 1H-NMR spectrum of [(Fe(H2HAPP)Cl2]Cl in D2O at 300K…. ………...........................................63
附圖五. 1H-NMR spectrum of [(Fe(H2HAPP)Cl2]Cl in D2O at 308K………….............................................64
附圖六. 1H-NMR spectrum of [(Fe(H2HAPP)Cl2]Cl in D2O at 318K …………............................................65
附圖七. 1H-NMR spectrum of [(Fe(H2HAPP)Cl2]Cl in D2O at 328K………….............................................66
附圖八. 1H-NMR spectrum of [(Fe(H2HAPP)Cl2]Cl in D2O at 338K …………............................................67
附圖九. 1H-NMR spectrum of [(Fe(H2HAPP)Cl2]Cl in D2O at 348K……………...........................................68
附圖十. 1H-NMR spectrum of [(Fe(H2HAPP)Cl2]Cl in D2O at 358K …………............................................69
附圖十一. 1H-NMR spectrum of [(Fe(H2HAPP)Cl2]Cl in D2O at 300K (after heat)...……………………………………………….70

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