臺灣博碩士論文加值系統

本研究透過鋅鹽、萘醯亞胺雙吡啶橋接配體N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide （NI-mbpy-34）和二酸 (對苯二酸、2-胺基對苯二酸、2-硝基對苯二酸)利用溶劑熱反應合成出一系列金屬有機框架化合物 [Zn2(1,4-bdc)2(NI-mbpy-34)] (1，1,4-H2bdc = benzene-1,4-dicarboxylic acid)、[Zn2(NH2-1,4-bdc)2(NI-mbpy-34)] (2，NH2-1,4-H2bdc = 2-aminobenzene-1,4-dicarboxylic acid)、[Zn(NO2-1,4-bdc)(NI-mbpy-34)] (3，NO2-1,4-H2bdc = 2-nitrobenzene-1,4-dicarboxylic acid)。化合物1為具有孔洞性的三角稜柱型二維層狀結構，孔洞佔有率為24.8%。化合物2為具有孔洞性的簡單立方型三維層柱狀結構，具有二次互穿的特性，孔洞佔有率為27.0%。化合物3為簡單立方型三維層柱狀結構，不具有孔洞性。
　 化合物1、2表現出對CO2及N2的吸附能力，化合物1、2在195K、P/P0 = 1時對CO2的吸附值分別為69.5 cm3/g、94.4 cm3/g，在77K、P/P0 = 1時對N2的吸附值分別為24.7 cm3/g、9.5 cm3/g。
化合物1、3可用於偵測硝基化合物。有機金屬框架與硝基化合物透過分子間π–π作用力或是氫鍵彼此靠近，經電子轉移機制將主框架的電子轉移至缺電子的硝基化合物上，造成螢光焠熄，達到偵測的效果。螢光感測實驗證實化合物1、3之甲醇懸浮液加入2-硝基苯酚，3-硝基苯酚，4-硝基苯酚，4-硝基甲苯，2,4-二硝基甲苯和1,4-二硝基苯有明顯的螢光焠熄，但是加入硝基苯和烷基類硝基化合物如硝基甲烷和2,3-二甲基-2,3-二硝基丁烷則無法有相同的螢光焠熄效應，具有選擇性感測的潛力。
我們也研究了有機金屬框架化合物1和3對蒸氣相硝基及有機小分子的吸附能力，實驗結果顯示並無明顯的螢光焠熄表現，因此沒有感測能力。
　 對氣相碘分子之吸附研究顯示化合物1可吸附碘分子後並造成螢光焠熄達到50%以上，晶體顏色也明顯的轉變為咖啡色。此外，碘分子亦可完全自化合物1脫附，使化合物1具有重複使用的潛力。

　A series of fluorescent metal－organic frameworks (MOFs) [Zn2(1,4-bdc)2(NI-mbpy-34)] (1, 1,4-H2bdc = benzene-1,4-dicarboxylic acid)、[Zn2(NH2-1,4-bdc)2(NI-mbpy-34)] (2, NH2-1,4-H2bdc = 2-aminobenzene-1,4-dicarboxylic acid)、[Zn(NO2-1,4-bdc)(NI-mbpy-34)] (3, NO2-1,4-H2bdc = 2-nitrobenzene-1,4-dicarboxylic acid) consisting of Zn(II), N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-34), and dicarboxylates were synthesized. Compound 1 is a 2D layer structure of trigonal prismatic cages with porosity of 24.8%. Compound 2 is a 3D primitive cubic type pillared-layer framework with porosity of 27.0%, which is 2-fold interpenetration. Compound 3 is a 3D nonporous primitive cubic type pillared-layer framework.
　Compounds 1 and 2 have shown moderate CO2 adsorption abilities, with values of 69.5 cm3/g and 94.4 cm3/g, respectively, at 195 K and P/P0 = 1, but poor N2 uptakes, with values of 24.7 cm3/g and 9.5 cm3/g, respectively, at 77 K and P/P0 = 1. After adding nitro compounds to methanol suspensions of 1 and 3, their luminescence emissions would be efficiently quenched by a series of nitroaromatics, involving 2-nitrophenol (2-NP), 3-nitrophenol (3-NP), 4-nitrophenol (4-NP), 4-nitrotoluene (4-NT), 2,4-dinitrotoluene (2,4-DNT) and 1,4-dinitrobenzene (1,4-DNB), but not by nitrobenzene (NB) and aliphatic nitro compounds, such as nitromethane (NM) and 2,3-dimethyl-2,3-dinitrobutane (DMNB).
We have further studied on vapor-sensing of 1 and 3 toward volatile nitro and organic compounds. The results show that the emissions of zinc MOFs did not effectively affected by both series of analytes, leading to inefficient detection for volatile nitro and organic compounds.
Studies on adsorption of volatile iodine showed that 1 can adsorb iodine molecules, resulting in significant crystal color change from colorless to brown and more than 50% fluorescence quenching.

摘要.................................................................................................................................i
Abstract.........................................................................................................................iii
目次................................................................................................................................v
表目次.........................................................................................................................viii
圖目次...........................................................................................................................ix
第一章 緒論…………………………………………………………………………1
1-1 超分子化學………………………………………………………………….1
1-1-1氫鍵(hydrogen bonding)………………..……………………….........2
1-1-2 π‒π 作用力 (π–π stacking) ……………………………….…………2
1-1-3凡得瓦力 (van der Waals forces) ……………………………………3
1-2 分子自組裝…………………………………………….…………………… 5
1-3 金屬有機框架 (Metal－Organic Framework，MOF)…………..………… 7
1-4 氣體吸附及相關文獻………………………………………………………. 8
1-5 硝基化合物感測及相關文獻…………………………………………… 10
1-6 有機小分子的感測及相關文獻…………………………………………...13
1-7 碘的吸附及相關文獻…………………………………………………… 14
1-8 水熱合成法………………………………………………………………... 16
第二章 研究動機…………………………………....................................................17
第三章 實驗部分…………………………………………………………………… 18
3-1 儀器………………………………………………………………………... 18
3-2 藥品………………………………………………………………………... 19
3-3 合成反應…………………………………………………………………... 21
第四章 結果與討論……………………………………………………..…………..27
4-1 化合物1之結構與物性探討 ……………………………………………...27
4-2 化合物2之結構與物性探討……………………………………………... 32
4-3 化合物3之結構與物性探討……………………………………………... 37
4-4 化合物1、2對CO2吸附能力探討…………………………………………42
4-5 化合物1、3之懸浮液對硝基化合物之螢光感測…………………………45
4-6 化合物1、3對硝基化合物之蒸氣吸附螢光感測………………………... 59
4-7 化合物1、3對有機小分子之氣相螢光感測………………………………62
4-8 化合物1、3對碘蒸氣吸附之螢光感測…………………….………...……65
第五章 結論………………………………………………………………………… 70
參考文獻…………………………………………………………………………….. 71
附錄………………………………………………………………………………….. 75
附錄1 1H NMR 圖譜………………………………………………………….. 75
附圖1-1 化合物NI-mpy-Br之1H-NMR (DMSO-d6) 圖譜…….…...…75
附圖1-2 化合物NI-mbpy-34之1H-NMR (DMSO-d6) 圖譜…...…… 76
附錄2 MALDI-TOF 質譜圖 …………………………………………………77
附圖2-1 化合物NI-mpy-Br之質譜圖………………………………….. 77
附圖2-2 化合物NI-mbpy-34之質譜圖………………………………… 78
附錄3 紅外線光譜圖..………………………………………………….……..79
附圖3-1 NI-mpy-Br之紅外線光譜圖…………………………………..79
附圖3-2 NI-mbpy-34之紅外線光譜圖…………………………………80
附圖3-3 化合物1之紅外線光譜圖 ……………………………………..81
附圖3-4 化合物2之紅外線光譜圖…………………………………….. 82
附圖3-5 化合物3之紅外線光譜圖…………………………………….. 83
附錄4 元素分析……………………………………………………………… 84
附圖4-1 NI-mpy-Br (20170414-OU-1)之元素分析...................................84
附圖4-2 NI-mbpy-34 (20170414-OU-2)之元素分析.................................85
附圖4-3 化合物1 (180320-BXY-Chu477) 之元素分析(樣品加熱去除客
分子)………………...………………………………………..…86
附圖4-4 化合物2 (180320-BXY-Chu456) 之元素分析(樣品加熱去除客
分子)…………………………………………………...……..…87
附圖4-5 化合物3 (180320-BXY-Chu520) 之元素分析(樣品加熱去除客
分子)………………………………………………...………..…88
附錄5 晶體數據………………………………………………………………. 89
附表5-1-1 化合物1之X光單晶繞射實驗數據條件……………………89
附表5-1-2 化合物1之原子位置參數…….…………………...…………90
附表5-1-3 化合物1之鍵長及鍵角……..………….………….…………92
附表5-1-4 化合物1之熱運動參數……………….…………..………….98
附表5-2-1 化合物2之X光單晶繞射實驗數據條件…….…....….……100
附表5-2-2 化合物2之原子位置參數……………..................................101
附表5-2-3 化合物2之鍵長及鍵角………………..…..……….……….103
附表5-2-4 化合物2之熱運動參數…………………………...………...108
附表5-3-1 化合物3之X光單晶繞射實驗數據條件…...……..…….…109
附表5-3-2 化合物3之原子位置參數…………….…………..…….......110
附表5-3-3 化合物3之鍵長及鍵角…………………….……...………..113
附表5-3-4 化合物3之熱運動參數…………….……………...…….….121

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