本篇論文主要是探討藉由2，6-吡啶二甲酸與4、4’與4”位置經1，1-二甲基乙基(新丁基)修飾過的參吡啶螯合上釕金屬所形成的端點分子團在以富碳的乙炔分子橋接下所形成之雙核釕金屬錯合物的合成，並透過核磁共振光譜、基質輔助雷射脫附質譜、傅氏轉換紅外線光譜、電化學與紫外吸收光譜等完成性質鑑定。而在與過去文獻中的雙參吡啶釕金屬橋接多乙炔基的錯合物系統比較電化學行為時，我們發現相較其僅一組金屬的氧化還原訊號，導入2，6-吡啶二甲酸為配位基的系統後在單乙炔基橋接下有一組不可逆(E1/2為1.15 V)與一組可逆(E1/2為0.59 V)的釕金屬氧化還原訊號；而同樣的情形也可以在雙乙炔基橋接的案例中被觀察到(不可逆峰的E1/2位置為1.10 V，可逆峰的E1/2位置為0.62 V)，這暗示著這樣的系統可使兩釕金屬中心間有不小的交互作用。此外，綜合電子光譜與電化學的證據顯示兩金屬中心間的交互作用會隨乙炔基數目增加而衰減。

The ruthenium dinuclear complexes with end-caping of pyridinedicarboxylate complexes of terpyridine (2,2':6',2'-terpyridine) and (tBu)3-terpyridine (4,4’,4’’-tri-tert-butyl-2,2’:6’,2’’-terpyridine) bridging with carbon-rich alkynyl group are reported. These novel complexes are characterized by NMR, MALDI-MS, FT-IR, UV, and electrochemistry. In comparison with the system of tpy-Ru-tpy-(≡)n-tpy-Ru-tpy, we found some interesting characteristics in the studies of electronic spectra and electrochemical measurements. Furthermore, one reversible and one irreversible electrochemical redox waves in positive wave were observed (E1/2 at 0.59 and 1.15 V (irrev.) for the complex with ethynyl spacer and E1/2 at 0.62 and 1.10 V (irrev.) for the complex with butynyl spacer), indicating a strong electronic interaction between two Ru metal centers. However, in the tpy-Ru-tpy-(≡)n-tpy-Ru-tpy system, only one electrochemical redox wave at ~1.3 V was found. From the electronic and electrochemical analysis , the electronic interaction between two metal centers decreases as the number of alkynyl group increases.

目錄..............................................................................................................i
圖目錄........................................................................................................iii
表目錄..........................................................................................................v
附錄.............................................................................................................vi

第一章 緒論
1-1 前言.....................................................................................................1
1-2 多吡啶金屬錯合物在分子導線中的發展.........................................5
1-3 以三重鍵為橋接基的參吡啶釕金屬錯合物.....................................6
1-4 以二茂鐵及二茂鐵三重鍵的參吡啶釕金屬錯合物.........................8
1-5 研究目的...........................................................................................10

第二章 實驗部分
2-1 藥品部分...........................................................................................14
2-2 儀器與物性測量方法.......................................................................15
2-3 合成部分...........................................................................................17
1 化合物14之合成............................................................................18
2 化合物15之合成............................................................................19
3 化合物16之合成.............................................................................19
4 化合物17之合成.............................................................................20
5 化合物18之合成.............................................................................20
6 化合物19之合成.............................................................................21
7 化合物20之合成.............................................................................21
8 化合物21之合成.............................................................................22
9 化合物22之合成.............................................................................23

第三章 結果與討論
3-1 合成方法探討...................................................................................24
3-2 雙核釕金屬錯合物的鑑定...............................................................28
3-3 紫外吸收光譜結果的探討...............................................................37
3-4 電化學行為的探討...........................................................................40

第四章 結論............................................................................................46

第五章 未來發展....................................................................................47

第六章 參考文獻....................................................................................49

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