臺灣博碩士論文加值系統

由不同環狀結構所構成的大環卟啉會具有不同的物理化學特性及不同的固態結構，雖然大環卟啉的合成產率不高，但仍然可以利用適當的起始物進行縮合反應，得到預期的大環卟啉結構，且近幾年來大環卟啉的化學研究迅速發展，也具有廣泛的應用研究，如：太陽能電池、綠色催化、配位化學、陰/陽離子鍵結偵測、光動力治療(Photodynamic therapy)、顯影劑(MRI, Magnetic Resonance Imaging)等。
在本論文中描述含硫原子修飾的六卟啉與八卟啉紫質大環化合物之合成、結構鑑定及潛在應用探討，因此我們根據大環卟啉的環大小將研究分為六卟啉與八卟啉兩大部分。
第一部分，合成含三硫三氮的六卟啉紫質大環化合物[28]-N3S3-hexaphyrins(1,1,1,1,1,1)，且發現在不同濃度BF3·Et2O的催化下，會有[30]-N3S3-hexaphyrins(1,1,1,1,1,1)的產生，而兩者間可藉由還原劑及氧化劑的作用相互轉換；結構鑑定則利用1D 1H、13C NMR、2D 1H-1H COSY、1H-13C HSQC NMR光譜及X-ray單晶結構進行，不同於一般的Hexaphyrins，[28]-N3S3-hexaphyrins(1,1,1,1,1,1)環外部的1H-NMR訊號位於upfield區域而環內部的1H-NMR訊號位於downfield區域，顯示其為一antiaromatic化合物，並利用NICS(Nucleus-Independent Chemical Shifts)證明其antiaromatic性質；此外我們也對於[28]-N3S3-hexaphyrins(1,1,1,1,1,1)進行配位化學、質子化的探討，在質子化方面結果顯示，質子化有可能造成結構大幅改變，最後，對於[28]-N3S3-hexaphyrins(1,1,1,1,1,1)進行陰離子作用的測試，發現[28]-N3S3-hexaphyrins(1,1,1,1,1,1)對於氟離子可能具有專一性的辨識效果。
第二部分，合成含四硫四氮的八卟啉紫質大環化合物[38]-N4S4-octaphyrins(1,1,1,1,1,1,1,1)，並藉由1D 1H、13C NMR、2D 1H-1H COSY、1H-13C HSQC、1H-13C HMBC NMR光譜及X-ray單晶結構進行結構鑑定，並探討質子化對於[38]-N4S4-octaphyrins(1,1,1,1,1,1,1,1)結構的影響；[38]-N4S4-octaphyrins(1,1,1,1,1,1,1,1) 藉由還原劑及氧化劑的作用，可發現其具有兩種不同的氧化還原，分別為38π到36π的轉換及38π到40π的轉換，並藉由UV-Vis光譜及NMR光譜探討其結構與芳香性的改變。

The expanded porphyrins composed of different ring structures will have different physical, chemical properties and different solid-state structures. Although the yield of expanded porphyrins is not high, a suitable starting material can be used for the condensation reaction. The expected expanded porphyrin structure has been obtained. In recent years, the research of expanded porphyrins has developed rapidly and has also been widely applied to solar cells, green catalysis, coordination chemistry, anion/cation binding, photodynamic therapy, and magnetic resonance imaging.
In this thesis, we describe the synthesis, structure identification and potential application of sulfur-containing hexaphyrin and octaphyrin. We divided the study into two parts of hexaphyrins and octaphyrins based on the ring size of eapanded porphyrins.
In the first part, we successfully synthesized heteroatom substituted expanded porphyrins, [28]-N3S3-hexaphyrins (1,1,1,1,1,1) and found that in different concentrations of BF3·Et2O, [30]-N3S3- hexaphyrins (1,1,1,1,1,1) can be generated. [28] & [30]-N3S3 are interconvertable with reducing agent or oxidizing agent. The identity of compounds are collaborate by 1D 1H, 13C NMR, 2D 1H-1H COSY, 1H-13C HSQC NMR spectroscopy and X-ray single crystal structural determination. Different from the general Hexaphyrin, the 1H-NMR signal of inner and outer [28] -N3S3-hexaphyrin ring is located in the upfield region and downfield region, respectively indicating that it is an antiaromatic compound, and it’s antiaromatic property was confirmed by NICS (Nucleus-Independent Chemical Shifts). In addition, we also studied [28]-N3S3-hexaphyrin (1,1,1,1,1,1) on the coordination chemistry and protonation. The protonation results show that protonation may cause structural changes. Finally, [28]-N3S3-hexaphyrin (1,1,1,1,1,1) was tested for anion binding and found [28]-N3S3-hexaphyrin (1,1,1,1,1, 1) may have binding specificity for fluorine ions.
In the second part, we successfully synthesized heteroatom sutituted expanded porphyrins, [38]-N4S4-octaphyrins (1,1,1,1,1,1,1,1) and confirmed by 1D 1H, 13C NMR, 2D 1H-1H COSY, 1H-13C HSQC, 1H-13C HMBC NMR spectroscopy and X-ray single crystal structure. The structure changes for [38]-N4S4-octaphyrin (1,1,1,1,1,1,1,1) by protonation were discussed. In addition, we found that [38]-N4S4-octaphyrin (1,1,1,1,1,1,1,1) can be interconverted by treating reducing agent or oxidizing agent to give either 36π or 40π electron state. Their structure and aromaticity changes are explored by UV-Vis and NMR spectroscopy.

摘要 I
Abstract III
目錄 V
圖目錄 IX
表目錄 XIII
式目錄 XIV
第一章 緒論 1
I. 關於紫質(porphyrin) 1
II. 紫質的衍生物 2
1. 氮異構紫質(Inversion porphyrin) 3
2. 收縮紫質(Contracted porphyrin) 4
3. 環異原子修飾紫質(Core-modified porphyrin) 4
4. 大環紫質(Expanded porphyrin) 5
III. 合成大環紫質 5
1. Rothemund & Lindsey 縮合反應 6
2. MacDonald-type縮合反應 6
3. Mcmurry-type reductive coupling 6
4. 鏈狀化合物環化反應 7
IV. 大環紫質的應用 7
1. 顯影劑( MRI, Magnetic Resonance Imaging) 8
2. 金屬離子配位化學 8
3. 陰離子鍵結(Anion binding) 9
第二章 N3S3 - Hexaphyrins的合成及結構鑑定 10
I. 前言 10
II. 實驗步驟 15
實驗藥品 15
儀器 15
合成步驟 17
2,5-Bis(2,6-dichlorobenzylhydroxymethyl)thiophene (Cl2-diol) (1a) 17
2,5-Bis(mesitylhydroxymethyl)thiophene (M-diol) (1b) 18
2,5-Bis(pentafluorobenzylhydroxymethyl)thiophene (PF-diol) (1c) 19
2,5-Bis(tolylhydroxymethyl)thiophene (tolyl-diol) (1d) 20
[28] 5,10,15,20,25,30-Hexa(2,6-dichlorophenyl)-31,33,35-trithia-hexaphyrin (1,1,1,1,1,1) (Cl2-N3S3) (3a) 21
[30] 5,10,15,20,25,30-Hexa(2,6-dichlorophenyl)-31,33,35-trithia-hexaphyrin (1,1,1,1,1,1) (Cl2-N3S3) (3’a) 22
[28] 5,10,15,20,25,30-Hexamesityl-31,33,35-trithia-hexaphyrin (1,1,1,1,1,1) (M-N3S3) (3b) 23
[28] 5,10,15,20,25,30-Hexa(pentafluorophenyl)-31,33,35-trithia-hexaphyrin (1,1,1,1,1,1) (PF-N3S3) (3c) 24
[28] 5,10,15,20,25,30-Hexatolyl-31,33,35-trithiahexaphyrin (1,1,1,1,1,1) (tolyl-N3S3) (3d) 25
III. 實驗結果與討論 26
1. Diols的合成與光譜鑑定 26
2. N3S3-Hexaphyrins的合成 28
3. N3S3-Hexaphyrins UV-vis光譜 32
4. [28]-N3S3-Hexaphyrins NMR光譜鑑定 36
5. [28]-N3S3-Hexaphyrins NICS(Nucleus-Independent Chemical Shifts) 41
6. [28]-N3S3-Hexaphyrins電化學光譜 43
7. [28]- N3S3-Hexaphyrin X-ray單晶結構 45
8. [28]-N3S3-Hexaphyrin之配位化學研究 48
9. [28]-N3S3- Hexaphyrin之質子化光譜及結構鑑定 51
10. [28]-N3S3- Hexaphyrin之應用 55
IV. 結論 59
第三章 N4S4- Octaphyrin的合成及結構鑑定 61
I. 前言 61
II. 實驗步驟 68
實驗藥品 68
儀器 68
合成步驟 70
[38] 5,10,15,20,25,30,35,40-Octa(2,6-dichlorophenyl)-31,33,35,37-tetrathia-octaphyrin (1,1,1,1,1,1,1,1) (Cl2-N4S4) (4a) 70
[38] 5,10,15,20,25,30,35,40-Octamesityl-31,33,35,37-tetrathia-octaphyrin (1,1,1,1,1,1,1,1) (M-N4S4) (4b) 71
[38] 5,10,15,20,25,30,35,40-Octatolyl-31,33,35,37-tetrathia-octaphyrin (1,1,1,1,1,1,1,1) (tolyl-N4S4) (4d) 72
III. 實驗結果與討論 73
1. N4S4-Octaphyrin合成 73
2. N4S4-Octaphyrin UV-vis光譜 74
3. [38]-N4S4-Octaphyrin NMR光譜鑑定 76
4. [38]-N4S4-Octaphyrin X-ray單晶結構 86
5. [38]-N4S4-Octaphyrin之質子化光譜及結構鑑定 87
6. [38]-N4S4-Octaphyrin氧化還原芳香性之探討 89
IV. 結論 94
第四章 未來工作與展望 95
參考資料 99
附 錄 104

 
圖目錄
圖1- 1 生物系統中紫質類金屬蛋白 1
圖1- 2 Heme攜氧前後結構 2
圖1- 3 紫質與紫質原 2
圖1- 4 Porphyrin衍生物的分類 3
圖1- 5 TPPH2、NCTPP之結構 3
圖1- 6 corrole之結構 4
圖1- 7 expanded porphyrins之結構 5
圖1- 8 Sessler’s group texaphyrin 8
圖1- 9具細胞顯影效果之expanded porphyrin 8
圖1- 10 Expanded porphyrin 金屬離子配位化學 9
圖1- 11 Sapphyrin’s fluoride binding 9

圖2- 1 Cavaleiro合成meso位置具pentafluorophenyl之N6 -hexaphyrins 11
圖2- 2 N6-[26]hexapentafluorohexaphyrin[1,1,1,1,1,1]之命名 12
圖2- 3 diols的結構 27
圖2- 4 Cl2-diol、M-diol、PF-diol及tolyl-diol之400MHz 1H-NMR光譜 27
圖2- 5 Mestiyl-hexaphyrin粗產物質譜 31
圖2- 6 Cl2-diol EI-Mass圖譜(上：Cl2diol+BF3·Et2O(crude product), 下：Cl2diol) 32
圖2- 7 Red-N3S3及Purple-N3S3之推測結構 33
圖2- 8 N3S3-hexaphyrins Uv-vis光譜(紅：[28]-Cl2-N3S3、綠：[28]-M-N3S3、褐：[28]-PF-N3S3、紫：[30]-Cl2-N3S3) 34
圖2- 9 [28]-Cl2-N3S3及[30]-Cl2-N3S3顏色變化 36
圖2- 10 [28]-Cl2-N3S3-hexaphyrin以NaBH4還原之UV-Vis光譜變化圖 36
圖2- 11 [30]-Cl2-N3S3-hexaphyrin以DDQ氧化之Uv-vis光譜變化圖 36
圖2- 12 Aromatic and antiaromatic ring current effect 37
圖2- 13 [28]-Cl2-N3S3-hexaphyrin’s 1H-NMR光譜 38
圖2- 14 [28]-Cl2-N3S3-Hexaphyrin之1H-13C HSQC光譜(CD2Cl2) 39
圖2- 15 [28]-Cl2-N3S3-Hexaphyrin之1H-1H COSY光譜(CD2Cl2) 40
圖2- 16 [28]-Cl2-N3S3-Hexaphyrin之NMR化學位移位置 41
圖2- 17 [28]-N3S3-Hexaphyrins及[26]-A4B2-N6之理論計算結構 42
圖2- 18 [28]-N3S3-hexaphyrins 1H-NMR光譜 43
圖2- 19 [28]- N3S3-hexaphyrins CV光譜 45
圖2- 20 [28]-Cl2-N3S3-Hexaphyrin單晶結構(俯視圖) 46
圖2- 21 [28]-M-N3S3-Hexaphyrin單晶結構(俯視圖) 46
圖2- 22 [28]-Cl2-N3S3-hexaphyrin外翻pyrrole環與分子平均平面夾角(側視圖) 47
圖2- 23 [28]-M-N3S3-hexaphyrin外翻pyrrole環與分子平均平面夾角(側視圖) 47
圖2- 24 [28]-Cl2-N3S3-hexaphyrin環內氮原子與硫原子與分子中心的距離 48
圖2- 25 [28]-Cl2-N3S3-hexaphyrin環內氮原子與硫原子與分子中心的距離 48
圖2- 26 N6-hexaphyrins金屬錯合物 49
圖2- 27 Pd3-Cl2-N3S3 UV-vis光譜 50
圖2- 28 Pd2-Cl2-N3S3 UV-vis光譜 50
圖2- 29 {[28]-Cl2-N3S3}(HClO4)n & {[28]-Cl2-N3S3}(TFA)n UV-Vis光譜 53
圖2- 30 {[28]-Cl2-N3S3}2+(ClO4-)2單晶結構(俯視圖) 54
圖2- 31 {[28]-Cl2-N3S3}2+(ClO4-)2單晶結構(側視圖) 54
圖2- 32 {[28]-Cl2-N3S3}2+(ClO4-)2 thiophene環與分子平面夾角 55
圖2- 33 [28]-Cl2-N3S3陰離子binding溶液顏色變化(不加入H2SO4(aq)) 56
圖2- 34 [28]-Cl2-N3S3陰離子binding UV-Vis光譜 (不加入H2SO4(aq)) 57
圖2- 35 [28]-Cl2-N3S3質子化&陰離子binding溶液顏色變化(加入H2SO4) 57
圖2- 36 [28]-Cl2-N3S3質子化&陰離子binding UV-Vis光譜 57
圖2- 37 [28]-Cl2-N3S3陰離子binding溶液顏色變化 58
圖2- 38 [28]-Cl2-N3S3陰離子binding UV-Vis光譜 58

圖3- 1 [36]-octaphyrin(2,1,0,1,2,1,0,1)之結構 61
圖3- 2 Möbius strip comforamation示意圖 65
圖3- 3 Hückel與Möbius分子系統 65
圖3- 4 Hückel & Möbius di-p-benzi[28]-hexaphyrin(1,1,1,1,1,1,)結構 66
圖3- 5 meso-aryl-substituted expanded porphyrin’s metalation 67
圖3- 6 meso-aryl-substituted [32]heptaphyrin(1,1,1,1,1,1,1) 67
圖3- 7 meso-aryl-substituted [32]heptaphyrin及[36]octaphyrin與TFA氫鍵作用 67
圖3- 8 N4S4-octaphyrins推測之共振結構 75
圖3- 9 Cl2-N4S4-octaphyrin與Cl2-N3S3-hexaphyrin Uv-vis光譜比較 76
圖3- 10 [38]-Cl2-N3S3-octaphyrin’s 1H-NMR光譜 77
圖3- 11 [38]-Cl2-N3S3-octaphyrin’s三種氫原子(左：pyrrole環的NH；中：pyrrole及thiophene環的β-H；右：dichlorophenyl取代基的Hmeta及Hpara) 77
圖3- 12 [38]-Cl2-N3S3-octaphyrin’s 1H-13C HSQC光譜(CDCl3) 78
圖3- 13 ｢8｣字型的[38]-Cl2-N4S4-octaphyrin分子對稱面 79
圖3- 14 [38]-Cl2-N3S3-octaphyrin’s 1H-1H COSY光譜(CDCl3) 80
圖3- 15 [38]-Cl2-N3S3-octaphyrin’s β-Hpyrrole及β-Hthiophene的化學位移 80
圖3- 16 [38]-Cl2-N3S3-octaphyrin’s 1H-13C HSQC(紅)及1H-13C HMBC(黑)光譜疊圖 82
圖3- 17 [38]-Cl2-N3S3-octaphyrin’s 1H-13C HSQC(紅)及1H-13C HMBC(黑)光譜疊圖 84
圖3- 18 [38]-Cl2-N3S3-octaphyrin’s 1H-1H COSY光譜(CDCl3) 85
圖3- 19 [38]-Cl2-N3S3-octaphyrin’s 1H-NMR光譜 85
圖3- 20 Free base [38]-Cl2-N4S4-octaphyrin單晶結構 86
圖3- 21 [38]-Cl2-N4S4-octaphyrin中心交叉pyrrole距離及平面夾角 87
圖3- 22 [38]-Cl2-N4S4-octaphyrin 質子化(HClO4)UV-vis光譜 87
圖3- 23 [38]-Cl2-N4S4-octaphyrin-HClO4單晶結構 89
圖3- 24 [38]-Cl2-N4S4-octaphyrin-HClO4 pyrrole環與分子平面夾角 89
圖3- 25 [38]-Cl2-N4S4-octaphyrin-HClO4環內硫原子與分子中心的距離 89
圖3- 26 Cl2-N4S4-octaphyrin顏色變化 90
圖3- 27 Cl2-N4S4-octaphyrin’s [38]→[40] reductive UV-Vis光譜 91
圖3- 28 Cl2-N4S4-octaphyrin’s [40]→[38] oxidative Uv-Vis光譜 91
圖3- 29 Cl2-N4S4-octaphyrin’s [38]→[36] oxidative Uv-Vis光譜 91
圖3- 30 Cl2-N4S4-octaphyrin’s [36]→[38] reductive UV-Vis光譜 92
圖3- 31 [36]、[38]及[40]-Cl2-N4S4-octaphyrin 1H-NMR光譜 93

圖4- 1 [28]-Cl2-N3S3-SO3H-hexaphyrin LR-ESI-MS光譜 96
圖4- 2 Bis-hexaphyrin crude product LR-MALDI-MS(tripyrrane與xanthene-dialdehyde莫爾數比為2:1) 98
圖4- 3 Bis-hexaphyrin crude product LR-MALDI-MS(tripyrrane與xanthene-dialdehyde莫爾數比為1:1) 98
表目錄
表2- 1 Hexaphyrins管柱層析後產率及其他副產物產率 30
表2- 2 [28]-N3S3-Hexaphyrins及[26]-A4B2-N6之NICS(0)值 42

表3- 1 Octaphyrins產率及其他產物產率 74

 
式目錄
式1- 1 環內修飾紫質S2TPP及STPPH 4
式1- 2 利用Lindsey condensation合成expanded porphyrins 6
式1- 3 McDonald-type method [3+2]condensation 6
式1- 4 McMurry - type reductive coupling 7
式1- 5 oligopyrrole cyclization reaction 7

式2- 1 Gossauer 合成之 hexaphyrins 10
式2- 2 Dolphin首例合成出 meso-substituted hexaphyrin 11
式2- 3 Diol合成步驟 26
式2- 4 N3S3-hexaphyrins及其他副產物 28
式2- 5 Lindsey’s method：two-step, one-flask synthesis of meso-Substituted porphyrin 29
式2- 6 [28]-Cl2-N3S3及[30]-Cl2-N3S3氧化還原關係 36

式3- 1 合成[36]octaphyrin(2,1,0,1,2,1,0,1) 62
式3- 2 合成[34]octaphyrin(1,1,1,0,1,1,1,0) 62
式3- 3 合成[32]octaphyrin(1,0,1,0,1,0,1,0) 62
式3- 4 合成[32]octaphyrin(1,0,0,0,1,0,0,0) 62
式3- 5 合成[30]octaphyrin(0,0,0,0,0,0,0,0) 63
式3- 6 合成[34]octaphyrin(1,0,1,0,1,0,1,0) 63
式3- 7 合成[34]octaphyrin(1,1,0,0,0,1,1,0) 63
式3- 8 N4S4-octaphyrin合成途徑 73

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