臺灣博碩士論文加值系統

近年來，由於自組裝(self-assembly)的方法問世，使得超分子在合成、設計與應用方面有了大大的進展。而這類自組裝的超分子其設計主要是透過改變其金屬角形(metal corner)與橋接配位基(bridging ligand)，進而去改變其大小、形狀、以及物性化性。其中比較常使用的配位基主要是線形的pyrazine, 4,4’-bipyridine或是在雙?啶中間再加入修飾基，這類的配位基多半是比較剛性且不易彎曲的，因此在金屬角形所提供的配位鍵角為九十度時，較容易得到四核的超分子。
與一般的合成策略不同，本篇使用的是比較柔軟性的配位基，4-Py2S2BF4 (2,3,5,6-tetrafluoro-1,4 -bis(4-pyridylsulfenyl)benzene)與另兩個類似的配位基。利用這類含硫的雙?啶配基，與M(d-t-bpy)Cl2、M(bpy)Cl2 ( M=Pd、Pt )以及Re(CO)5Cl進行自組裝反應，並且透過X-ray單晶繞射鑑定出，這類較柔軟的配位基，較容易得到雙核的分子環形( molecular loop )。
另外，我們也將之應用於配位高分子( coordination polymer )的合成。在此，我們發現到由於其柔軟性，使其與鋅二價金屬位配時，得到另一個構形，而這個柔軟性主要是來自於碳-硫單鍵能夠自由旋轉所致。除了在結構的鑑定上，我們也去測量一些相關的吸收、放射光譜的性質，以期能應用於感測、辨識方面。

The strategy to construct supermolecules has been greatly improved as the self-assembly phenomena was discovered during last decades. The desired functionality in metalla-supramolecular squares may be introduced by employing functional ligands or properly functionalized metal corners with appropriate sizes and shapes. 4,4’-bipyridine is commonly used as a bridging ligand in generating a macrocyclic compound. Usually, tetranuclear compounds are formed when a rigid spacer such as 4,4’-bipyridine is used as a bridging ligand.
Unlike the conventional synthetic strategy, a flexible ligand, 4-Py2S2BF4 (2,3,5,6-tetrafluoro-1,4-bis(4-pyridylsulfenyl)benzene), was chosen as a bridging ligand for the construction of macrocyclic molecules with Pd(Ⅱ), Pt(Ⅱ), or Re(Ⅰ) ion as metal corners, respectively. The X-ray diffraction analysis shows that [Pd(d-t-bpy)(4-Py2S2BF4)]2(OTf)4 (1) (d-t-bpy=4,4’-di-tert-butyl-2,2’-bipyridine) forms a supramolecular-looped compound, where the supramolecular loops were also stacked to form interesting one-dimensional channels in the solid state.
Beside the supramolecular synthesis, we are also interested in the construction of interesting coordination polymers based on 4-Py2S2BF4. Here, the coordination polymer 7 was synthesized by using 4-Py2S2BF4 with ZnI2, characterized by the X-ray diffraction study. In addition, spectroscopic and photophysical properties of the compounds synthesized here were investigated.

總目錄
圖目錄………………………………………………………...Ⅲ
附圖目錄……………………………………………………...Ⅴ
表目錄…………………………………………………….......Ⅶ
附表目錄………………………..…………………………….Ⅶ

第一章　緒論 4
§ 1-1　超分子化學的起源與定義 4
§ 1-2　超分子結構的設計 8
§ 1-3　超分子化合物的應用 10
§ 1-4　研究動機 19
第二章 實驗部分 22
§ 2-1　實驗裝置及鑑定方法 22
§ 2-2　配位基的合成及鑑定 23
2,3,5,6-tetrafluro-1,4-bis(4-pyridylsulfenyl)benzene (4-Py2S2BF4) 23
2,3,5,6-tetrafluro-1,4-bis(2-pyridylsulfenyl)benzene (2-Py2S2BF4) 24
2,3,5,6-tetrafluro-1,4-bis(2-pyrimidylsulfenyl)benzene (2-Pym2S2BF4) 24
§ 2-3　金屬角形（Metal Corner）的合成 25
Pd(d-t-bpy)Cl2 25
Pt(d-t-bpy)Cl2 25
Pd(bpy)Cl2 26
Pt(bpy)Cl2 26
§ 2-4　金屬錯合物的合成…………………...….…...………..……..27
[Pd(d-t-bpy)(4-Py2S2BF4)]2(OTf)4 (1) 27
[Pd(d-t-bpy)( 2-Py2S2BF4)]2(OTf)4 (2) 28
[Pd(d-t-bpy)( 2-Pym2S2BF4)]2(OTf)4 (3) 28
[Pt(d-t-bpy)( 4-Py2S2BF4)]2(OTf)4 (4) 28
[Pd(bpy)( 4-Py2S2BF4)]2(NO3)4 (5) 29
[Re(CO)3Cl(4-Py2S2BF4)]2 (6) 30
§ 2-5 配位高分子的合成…………………….……...………..……..30
[ZnI2(4-Py2S2BF4)]‧EtOH (7) 30
第三章　結果與討論 31
§ 3-1 分子環形(MOLECULAR LOOPS)的合成 31
§ 3-2 配位高分子(COORDINATION POLYER)的合成 34
§ 3-3光譜和光物理性質 37
第四章　結論與未來展望 47
參考文獻 48

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