臺灣博碩士論文加值系統

本論文利用吡啶雙羧酸：3,5-Py(CO2H)2、2,3-Py(CO2H)2 、3,4-Py(CO2H)2 、2,5-Py(CO2H)2 作為配位基 (L) 和 [Cu2(dppm)2(MeCN)2](BF4)2 金屬起始物 (M) 合成環狀金屬錯合物：[Cu2(dppm)2(μ-(3,5-Py(CO2)2))]2(BF4)2 (3(BF4)2)、[Cu2(dppm)2(μ-(2,3-Py(CO2)2))]2(BF4)2 (4(BF4)2)、[{Cu2(dppm)2}2(μ-(3,4-Py (CO2)2))]2(BF4)4 (5(BF4)4)、[{Cu2(dppm)2}2(μ-(2,5-Py(CO2)))]2(BF4)4 (6(BF4)4)、{Cu2(dppm)2}2(μ-(3,5-Py(CO2)))]2(PF6)2 (7(BF4)2)，之後使用金屬起始物 [Ag2(dppm)2(MeCN)2](BF4)2 (M) 與 4-Py(CO2H) 合成[{Ag2(dppm)2}2(μ-(4-Py(CO2)))]n (BF4)n (9(BF4)n) 結構。這些結構藉由單晶X-光繞射儀與氫光譜圖、磷光譜圖以及紅外光譜圖確定有合成出來，而這些結構為雙聚物((3(BF4)2) 、4(BF4)2、5(BF4)4、6(BF4)4、7(BF4)2)以及一為維無限延伸的Z字形鏈狀結構(9(BF4)n)。
當在 [{Cu2(dppm)2}(μ-(4-Py(CO2))]4(PF6)4 (8(PF6)4) 一方型環狀結構中加入NH4PF6 分子時，進行分子辨識實驗時，得到令人振奮的結果，可以發現磷光圖譜以及紅外光圖譜與顏色都有明顯的變化，可以推測 8(PF6)4 可以辨識NH4PF6 分子。
接下來使用 [{Cu2(dppm)2}(μ-(4-Py(CO2))]4(BF4)4 與 4.4‘-bipyridine以機動化學方式進行擴環反應。當 [{Cu2(dppm)2}(μ-(4-Py(CO2))]4(BF4)4 跟不同比例的4.4‘-bipyridine 進行反應後，其磷光圖譜以及紅外光圖譜與顏色都有明顯的變化，可以認為應有新結構的生成。

In here,we successfully using the the combination of a flexible ligand-capped dinuclear transition-metal acceptor [Cu2(dppm)2(NCMe)2](BF4)2 with tritopic monodentate-bidentate donors such as 3,5-,2,3-, 3,4-, 2,5-pyridyldicarboxylates produced metallacycles like [Cu2(dppm)2(μ-(3,5-Py(CO2)2))]2(BF4)2 (3(BF4)2), [Cu2(dppm)2(μ-(2,3-Py(CO2) 2))]2(BF4)2 (4(BF4)2), [{Cu2(dppm)2}2(μ-(3,4-Py(CO2)2))]2 (BF4)4 (5BF4)4), [{ Cu4(dppm)4}(μ-(2,5-Py (CO2)2))]2(BF4)2(6(BF4)4), [{Cu2(dppm)2}2 (μ-(3,5-Py(CO2)))]2(BF4)4 (7(BF4)4). When we changed dinuclear transition-metal acceptor [Cu2(dppm)2(NCMe)2](BF4)2 metal centers from Cu(I) to Ag(I) and [Ag2(dppm)2](BF4)2 reacted with 4-pyridylcarboxylates, it become a 2-D zigzag polymer. All new copmlexes were characterized by liquid-state NMR, liquid-state IR spectra. Single-crystal structure of each complex were determined by single-crystal diffraction data.
We put the NH4PF6 molecular to react with metallacyclic [{ Cu2(dppm)2}(μ-(4-Py (CO2)2))]4(PF6)4(8(BF4)4) as a chemical sensing test,and we got a exciting result that the 31P NMR、H NMR peak shift dramatically and the solution’s colar change a lot too, it seem that 8(BF4)4 could act as chemical sensor.
Next, a ring expention of [{Cu2(dppm)2}(μ-(4-Py(CO2))]4(BF4)4 and 4.4'-bipyridine was carried out in dynamic Chemical method. Then we combinated [{Cu2(dppm)2}(μ-(4-Py (CO2)2))]4(BF4)4 with different proportion of 4,4‘-bipyridine the phosphorescence spectrum and the infrared spectrum and color of the reaction were changed obviously, it can be considered that a new structure should be generated.

摘要 i
Abstract ii
致謝 xii
目錄 xiii
表目錄 xvi
圖目錄 xviii
緒論 1
1.1自主裝(self-assembly method) 2
1.分子辨識： 3
2.組成成份 4
3.溶劑 6
4.熱力學平衡 7
1.2分子間的作用力 8
1.3 超分子環的合成 14
1.4機動化學 (Dynamic Chemistry) 23
1.5相關研究 27
1.6研究動機 47
實驗部分 50
2.1實驗操作 50
2.2儀器及其型號 51
2.3合成及鑑定 53
2.3.1起始物合成 54
2.3.2金屬錯合物合成 55
[Cu2(dppm)2(μ-(3,5-Py(CO2)2))]2(BF4)2 (3(BF4)2)的合成: 55
[Cu2(dppm)2(μ-(2,3-Py(CO2)2))]2(BF4)2 (4BF4)2)的合成: 56
[{Cu2(dppm)2}2(μ-(3,4-Py(CO2)2))]2 (BF4)4 (5BF4)4)的合成 57
[{Cu2(dppm)2}2(μ-(2,5-Py(CO2)))]2 (BF4)4 (6BF4)4)的合成 58
[{Cu2(dppm)2}2 (μ-(3,5-Py(CO2)))]2(BF4)4 (7(BF4)4)的合成 59
[Cu2(dppm)2(μ-(4-Py(CO2)))]4(PF6)4 (8(PF6)4)的合成 60
[{Ag2(dppm)2}2(μ-(4-Py(CO2)))]n (BF4)n (9(BF4)n)的合成 61
結果與討論 62
3.1 雙核金屬錯合物與吡啶羧酸的反應探討 62
3.2 雙合銅(I)錯合物與與吡啶雙羧酸所合成結構探討 79
3.3銀金屬與吡啶羧酸所合成結構 119
3.4 [{Cu2(dppm)2}(μ-(4-Py(CO2))]44+反應性探討 127
3.5 機動化學擴環反應的數據 131
4. 結論 135
附錄 136
1.各個結構氫譜圖、磷譜圖與IR圖譜 136
附錄圖一 3(BF4)2之氫譜圖 136
附錄圖二 3(BF4)2 磷譜圖 137
附錄圖三 3(BF4)2 IR圖譜 138
附錄圖四 4(BF4)2 氫譜圖 140
附錄圖五 4(BF4)2 磷譜圖 141
附錄圖六 4(BF4)2 IR圖譜 142
附錄圖七 5(BF4)4氫譜圖 144
附錄圖八 5(BF4)4磷譜圖 145
附錄圖九 5(BF4)4 IR圖 146
附錄圖十 6(BF4)4氫譜圖 148
附錄圖十一 6(BF4)4磷譜圖 149
附錄圖十二 6(BF4)4 IR 圖 150
附錄圖十三 7(PF6)4氫譜圖 152
附錄圖十四 7(PF6)4 磷譜圖 153
附錄圖十五 7(PF6)4 IR圖譜 154
附錄圖十六 8(PF6)4之氫譜圖。 156
附錄圖十七 8(PF6)4 磷譜圖 157
附錄圖十八 8(PF6)4 IR圖譜 158
附錄圖十九 9(BF4)n之氫譜圖。 159
附錄圖二十 9(BF4)n磷譜圖 161
附錄圖二十一 9(BF4)n IR圖譜 162
2.晶體數據 164
附表一 3(BF4)2 晶體資料 164
附表二 4(BF4)2 晶體資料 165
附表三 5(BF4)4 晶體資料 166
附表四 6(BF4)4 晶體資料 167
附表五 7(BF4)4 晶體資料 168
附表六 8(PF6)4 晶體資料 169
附表七 9(BF4)n 晶體資料 170
3.各晶體checkcif 171
[{Cu2(dppm)2}(μ-(3,5-Py(CO2)2))]2(BF4)2(3(BF4)2) 171
[{Cu2(dppm)2}(μ-(2,3-Py(CO2)2))]2(BF4)2(4(BF4)2) 174
[{Cu4(dppm)4}(μ-(3,4-Py (CO2)2))]2(BF4)2(5(BF4)4) 177
[{ Cu4(dppm)4}(μ-(2,5-Py (CO2)2))]2(BF4)2(6(BF4)4) 180
[{ Cu4(dppm)4}(μ-(3,5-Py (CO2)2))]2(BF4)2(7(BF4)4) 183
[{ Cu2(dppm)2}(μ-(4-Py (CO2)2))]4(PF6)4(8(BF4)4) 187
[{Ag2(dppm)2}(μ-(4-Py(CO2)))]n (BF4)n (9(BF4)n) 191
References 194

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