臺灣博碩士論文加值系統

本研究內容是以金屬離子與有機配基，利用自組裝（self-assembly）的方式來合成一系列的金屬有機骨架化合物(metal-organic frameworks, MOFs)。本篇研究使用4,4’,4’’-s-triazine-2,4,6-triyltribenzoic acid (p-TATB)為有機配基，與In(NO3)3合成{[In(p-TATB)(H2O)(DMSO)]•2DMSO}n (1)；用3,3’, 3’’-s-triazine-2, 4, 6-
triyltribenzoic acid (m-TATB)為有機配基，分別與Zn(NO3)2•6H2O合成{[Zn2(m-TATB)(H2O)2]•0.5(C2O4)•DMA}n (2)、In(Cl3)3 合成{(H2NEt2)[In(m-TATB)Cl]•1.5DEF•H2O}n (3)；用4-sulfobenzoic acid (4-SBA)為有機配基，與多種鑭系金屬合成{K2[Ln2(4-SBA)4(H2O)4]}n (Ln = Eu(4a)、Gd(4b)、Tb(4c)、Dy(4d)、Ho(4e)、Y(4f)、Eu+Tb(4g))。
X光單晶繞射(single-crystal X-ray diffraction)顯示1為四重交錯的三維結構，使用PLATON計算除去溶劑後的孔洞率為46.9%，但做溶劑交換除去DMSO，再除去水後並無法保持原本的結晶相；2為二重交錯的三維結構，孔洞率為34.4%，經溶劑交換後失去原本的相，但放回原溶劑後又產生另一新的相；3為二重交錯的三維結構，孔洞率為51.4%，做溶劑交換後成功除去DEF並保有原本的晶相。4a~4g則以Ln與4SBA連接成為二維結構，且為等結構，其中4a(Eu)、4c(Tb)、4d(Dy)、4e(Ho)、4g(Eu + Tb)在可見光區皆有鑭系特徵放光行為。

Here we report that the self-assembly of serveral metal ions and ligands leads to the formation of a series of metal-organic frameworks (MOFs). Different MOFs were obtained with the choice of the entitled ligands. 4, 4’, 4’’-s-triazine-2, 4, 6-triyltribenzoic acid (p-TATB) results in {[In(p-TATB)(H2O)(DMSO)]•2DMSO}n (1); 3, 3’, 3’’-s-triazine-2, 4, 6-triyltribenzoic acid (m-TATB) results in {[Zn2(m-TATB) (H2O)2]•0.5(C2O4)•DMA}n (2) and {(H2NEt2)[In(m-TATB)Cl]•1.5DEF•H2O}n (3); 4-sulfobenzoic acid (4-SBA) results in {K2[Ln2(4-SBA)4(H2O)4]}n (Ln = Eu(4a), Gd(4b), Tb(4c), Dy(4d), Ho(4e), Y(4f), Eu+Tb(4g)).
Single-crystal X-ray diffraction studies indicate 1 has four identical interwoven 3D nets with solvent-accessible volume of 46.9% calculated using PLATON, but when its solvent molecules are removed, 1 transforms to amorphous phase. 2 has two-fold interwoven 3D nets with solvent-accessible volume of 34.4%. After solvent exchange, 2 transforms to amorphous phase. Nevertheless, when 2 soaks in origin solvent, 2 transforms to another new phase. 3 also has two-fold interwoven 3D nets with solvent-accessible volume of 51.4%. Removing guest solvent molecules, the framework of 3 remains intact. 4a-4g are isostructures adopting 2D frameworks. Complexes 4a(Eu), 4c(Tb), 4d(Dy), 4e(Ho) and 4g(Eu+Tb) exhibit photoluminescent properties, giving characteristic Ln3+ emissions.

目錄 I
圖目錄 III
表目錄 IX
附圖目錄 X
附表目錄 XI
中文摘要 1
Abstract 2
第一章 緒論 3
第二章 有機-無機配位材料開發 15
2.1 實驗儀器 15
2.2 藥品來源 17
2.3 合成步驟 19
2.3.1 4, 4’, 4’’-s-triazine-2, 4, 6-triyltribenzoic acid (p-TATB) 19
2.3.2 3, 3’, 3’’-s-triazine-2, 4, 6-triyltribenzoic acid (m-TATB) 20
2.3.3 {In(p-TATB)(H2O)(DMSO)•2DMSO}n (1)之合成 21
2.3.4 {[Zn2(m-TATB)(H2O)2]•0.5(C2O4)•DMA}n (2)之合成 22
2.3.5 {(H2NEt2)[In(m-TATB)Cl]•1.5DEF•H2O}n (3)之合成 23
2.3.6 {K2[Ln2(4-SBA)4(H2O)4]}n [Ln = Eu (4a)、Gd (4b)、Tb (4c)、Dy (4d)、Ho (4e)、Y (4f)、Eu + Tb (4g)]之合成 24
2.4 X光單晶繞射實驗及構造解析 29
2.4.1 {In(p-TATB)(H2O)(DMSO)•2DMSO}n (1) 29
2.4.2 {[Zn2(m-TATB)(H2O)2]•0.5(C2O4)•DMA}n (2) 31
2.4.3 {(H2NEt2)[In(m-TATB)Cl]•1.5DEF•H2O}n (3) 33
2.4.4 {K2[Eu2(4-SBA)4(H2O)4]}n (4a) 35
2.4.5 {K2[Gd2(4-SBA)4(H2O)4]}n (4b) 37
2.4.6 {K2[Tb2(4-SBA)4(H2O)4]}n (4c) 39
2.4.7 {K2[Dy2(4-SBA)4(H2O)4]}n (4d) 41
2.4.8 {K2[Ho2(4-SBA)4(H2O)4]}n (4e) 43
2.4.9 {K2[Y2(4-SBA)4(H2O)4]}n (4f) 45
2.4.10 {K2[EuTb(4-SBA)4(H2O)4]}n (4g) 47
第三章 結果與討論 49
3.1 {[In(p-TATB)(H2O)(DMSO)]•2DMSO}n (1) 49
3.1.1 合成 49
3.1.2分子結構 50
3.1.3 紅外線光譜42 55
3.1.4 熱重分析 56
3.1.5 溶劑交換 59
3.2 {[Zn2(m-TATB)(H2O)2]•0.5(C2O4)•DMA}n (2) 62
3.2.1 合成 62
3.2.2 分子結構 63
3.2.3 紅外線光譜 67
3.2.4 熱重分析 68
3.2.5 溶劑交換與轉變 69
3.3 {(H2NEt2)[In(m-TATB)Cl]•1.5DEF•H2O}n (3) 71
3.3.1 合成 71
3.3.2 分子結構 72
3.3.3 紅外線光譜 76
3.3.4 熱重分析 77
3.3.5 溶劑交換與轉變 78
3.3.6 陽離子之鑑定 80
3.3.7 氣體吸脫附 84
3.4 {K2[Ln2(4-SBA)4(H2O)4]}n (Ln = Eu(4a), Gd(4b), Tb(4c), Dy(4d), Ho(4e), Y(4f), Eu+Tb(4g)) 85
3.4.1 合成 85
3.4.2 分子結構 86
3.4.3 紅外線光譜 90
3.4.4 熱重分析 91
3.4.5 固態放光光譜 93
第四章 結論 101
參考文獻 103
附圖 107
附表 122

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