臺灣博碩士論文加值系統

摘要
本論文中描述含三氮三硫的紫質大環化合物(RedN3S3、PurpleN3S3)及其衍生物(化合物8、化合物 9、Pd-N3S3)的合成及鑑定。RedN3S3及PurpleN3S3可經由不同濃度BF3Et2O催化再經DDQ氧化而得，所得的RedN3S3及PurpleN3S3可分別在還原劑及氧化劑的作用下相互轉換，不同於其他穩定存在的hexaphyrins，RedN3S3大環外部的NMR吸收鋒位置在高磁場的區域而內部的氫卻在低磁場的區域吸收，顯示RedN3S3為一antiaromatic compound。鹼基晶體結構顯示為一具有pyrrole及thiophene翻轉的方形結構，然而，從TFA雙質子化的方形結構到HClO4(aq)雙質子化後三角形結構，顯示質子化酸源的不同卻可造成結構大幅改變。
衍生物化合物 8及化合物 9可由RedN3S3鹼基與CuCl經由C-Cl及C-H鍵活化後而得到特殊的環化結構，同時，化合物 9的產率亦可經由置換CuCl為[Cu(CH3CN)4][BF4]而大幅提升，2個化合物的NMR光譜行為亦顯示為antiaromatic compound，而compound 8在室溫下NMR光譜呈現broaden現象，經動力學NMR測量可得翻轉的能量為61.65 kJ/mol，所得化合物 8晶體結構呈現方形和RedN3S3類似，內部(5,5,6)環遠離中心平面使得結構呈現扭曲。不同於化合物 8，經由dimethyl- amino group 植入的化合物 9呈現和RedN3S3 bis-hydroperchlorate salt相同三角形結構，其中以共價鍵鍵結的dimethylamino group對大環共振能的影響較以氫鍵鍵結的RedN3S3 bis-hydroperchlorate salt為巨。
N3S3-hexaphyrin的Pd錯合物可由具弱配位基的Pd(CH3CN)4[BF4]2與RedN3S3作用得到，其UV-vis光譜呈現紅移，晶體結構顯示為一個三金屬中心的化合物。

Abstract
Core-modified N3S3-hexaphyrins, their derivatives and metal complex of N3S3-hexaphyrin have been synthesized. Condensation of pyrrole with 2,5-bis(2,6-dichlorophenylhydroxymethyl) thiophene under Lindsey’s condition using different BF3Et2O concentrations resulted in the formation of [28]5,10,15,
20,25,30-hexa(2,6-dichlorophenyl)-31,33,35-trithiahexaphyrin[1,1,1,1,1,1],H1(RedN3S3) and [30] 5,10,15,20,25,30-hexa
(2,6-dichlorophenyl)-31,33,35-trithiahexaphyrin[1,1,1,1,1,1],H3(PurpleN3S3). The effect of catalysts, reaction concentrations, temperature and oxidants on the product distribution were examined by TLC analysis. Spectroscopic data showed that the reduced and oxidized N3S3-hexaphyrin are interconverterable with proper oxidants or reductants . The peaks of inner and outer protons observing at downfield and upfield shifts, respectively, revealed the antiaromatic characteristic of RedN3S3. Three X-ray structures, free base, bis-hydroperchlorate and bis-trifluoroacetate, were obtained and demonstrated the flexibility of N3S3-hexaphyrin.
The hexaphyrin deriatives, [28]5,10,15,20,25-penta
(2,6-dichlorophenyl)-30-(2-aza32-6-monochlorophenyl)-31,33,
35-trithiahexaphyrin[1,1,1,1,1,1], (compound 8) and C2-N1-[28]5,10,15,20,25,30-hexa(2,6-dichlorophenyl)-31,33,35-trithiahexaphyrin[1,1,1,1,1,1]-N4-methyl-methane (compound 9), were synthesized from refluxing the N3S3-hexaphyrin with CuCl in DMF. CuCl catalyzed C-Cl and C-H bond activation formed unusual (5,5,6) ring (compound 8) and (5,7,5) (compound 9) ring structure ,respectively. Both compounds have similar NMR spectroscopic properties as RedN3S3 and were determined to be antiaromatic compounds. The X-ray structure of compound 8 showed rectangular geometry similar to RedN3S3.with the (5,5,6) ring tilted out of main planar,while, X-ray structure of compound 9 revealed triangle geometry as RedN3S3 bis-hydroperchlorate. The chemical shifts showed that dimethylamino group which covalently bonded to RedN3S3 had more influence on resonance energy than compound 8.
The metal complex of RedN3S3, Pd-N3S3,had been synthesized. UV-vis absorption of 655 nm revealed bathochromic shift after metallation. As RedN3S3 bis-hydroperchlorate and compound 9, the X-ray structure of Pd-N3S3 showed triangle geometry.

目錄
頁次
Abstract 13
中文摘要 15
第一章 緒論 17
關於porphyrin 17
porphyrin 衍生物的分類 19
expanded porphyrins的功用 22
expanded porphyrins的合成方法 26
expanded porphyrins的種類 28
第二章 N3S3-Hexaphyrins的合成、結構鑑定及其
最佳化反應之研究 33
前言 33
實驗步驟 39
合成步驟 42
實驗結果與討論 45
diols合成及鑑定 45
N3S3-hexaphyrins合成 47
N3S3-hexaphyrins UV-vis光譜 52
RedN3S3-hexaphyrin NMR光譜 57
N3S3-hexaphyrins X-ray晶體結構 66
結論 71
第三章 RedN3S3-Hexaphyrin的質子化光譜及結構鑑定 73
前言 73
實驗步驟 74
實驗結果與討論 75
RedN3S3-HClO4及RedN3S3-TFA UV-vis光譜 75
RedN3S3-HClO4及RedN3S3-TFA X-ray晶體結構 77
結論 81
第四章 Cu(I)催化C-H及C-Cl鍵的活化以形成
N-fused-like N3S3-Hexaphyrins 83
前言 83
實驗步驟 86
實驗結果與討論 89
化合物 8合成 89
化合物 8 Uv-vis光譜 92
化合物 8 NMR光譜 93
化合物 8 X-ray晶體結構 100
化合物 9 合成 106
化合物 9 Uv-vis光譜 107
化合物 9 NMR光譜 108
化合物 9 X-ray晶體結構 116
推測之化合物8及化合物9生成之機構 122
結論 124
第五章 RedN3S3-Hexaphyrin之配位化學研究 126
前言 126
實驗步驟 129
實驗結果與討論 129
Pd-N3S3 合成 130
Pd-N3S3 UV-vis光譜 130
Pd-N3S3 X-ray晶體結構 132
結論 136
第六章 未來工作與展望 137
參考書目 142
Appendix 157

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