本篇論文主要是探討藉由帶負二價的 2，6-吡啶二甲酸與 4、4’ 與 4” 位置經新丁基修飾過的參吡啶螯合上鋨金屬並以富碳的乙炔分子橋接下所形成之中性雙核鋨金屬錯合物的合成，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並以鋨金屬微調在單乙炔基橋接下同樣只有一組可逆（E1/2 為 0.37 V）的鋨金屬氧化還原訊號，雖然這樣的分子導線系統使 HOMO-LUMO gap 縮小了但兩鋨金屬中心間仍舊不足以有很好的交互作用力。在 UV-Visible 吸收光譜方面，單核鋨金屬錯合物在可見光區有三組 MLCT 之特徵吸收峰；紫外光區也有三組配位基之特徵吸收峰，在雙核鋨金屬錯合物方面則是兩組 MLCT 之特徵峰以及三組紫外區的配位基之特徵吸收峰。

In this study, We used the pyridine-2,6-dicarboxylic acid and 4,4’,4’’-tri-tert-butyl-2,2’:6’,2’’-terpyridine and bridging with carbon-rich alkynyl group to form the neutral osmium dinuclear complexes. These novel complexes are characterized by NMR, MALDI-MS, FT-IR, UV, and electrochemistry. In comparison the electrochemistry of the tpy-Ru-tpy-(≡)-tpy-Ru-tpy system, we found use the pyridine-2,6-dicarboxylic acid as ligand and the metal is osmium and bridging with carbon-rich alkynyl group in the studies of electrochemical measurements, the metal center showed only one reversible redox wave at E1/2 = 0.37 V. Although in the tpy-Os-pydic-(≡)-pydic-Os-tpy system had small HOMO-LUMO gap, however the electronic interaction between two osmium centers still small. In the UV-Visible spectrum, we observed three MLCT absorption band of the osmium monomer complex at Visible region, and three absorption band of the ligand at UV region, the osmium dimer complex, we observed two MLCT absorption band at Visible region and three absorption band of the ligand at UV region.

目錄....................................................................................................................................i
圖目錄..............................................................................................................................iii
表目錄..............................................................................................................................iv
附錄圖...............................................................................................................................v

第一章 序論.....................................................................................................................1
1-1 前言............................................................................................................................1
1-2 以叁鍵為橋接基的參吡啶釕金屬分子導線............................................................2
1-3. 以 bis(2,6-dicarboxypyridine)-4-yl 為橋接基的釕金屬錯合物...........................10
1-4 鋨（Os）金屬中心.................................................................................................13
1-5 研究目的..................................................................................................................15
第二章 實驗部分...........................................................................................................16
2-1 藥品部分..................................................................................................................16
2-2 儀器與物性測量方法..............................................................................................17
2-3 合成部分..................................................................................................................19
2-3-1 化合物 12 之合成：...........................................................................................21
2-3-2 化合物 Os(tBu-tpy)(pydic) 之合成：................................................................21
2-3-3 化合物 13 之合成：...........................................................................................22
2-3-4 化合物 14 之合成：...........................................................................................22
2-3-5 化合物 15 之合成：...........................................................................................23
2-3-6 化合物 16 之合成：...........................................................................................24
2-3-7 化合物 11 之合成：...........................................................................................24
第三章 結果與討論.......................................................................................................26
3-1 合成方法..................................................................................................................26
3-2 化合物 Os(tBu-tpy)(pydic) 與 [Os(tBu-tpy)(pydic)]2 鑑定..................................27
3-3 電化學結果的探討..................................................................................................32
3-4 UV-Visible 光譜探討...............................................................................................36
第四章 結論...................................................................................................................39
第五章 參考文獻...........................................................................................................40
附錄.................................................................................................................................42

1. （a）Sutter, J. P.; Grove, D. M.; Beley, M.; Collin, J.-P.; Veldman, N.; Spek, A. L.; Sauvage, J.-P.; Koten, G. V. Angew Chem. Int. Ed. Engl. 1994, 33, 1282.（b）Martin, R. E.; Diederich, F. Angew Chem. Int. Ed. Engl. 1999, 38, 1350.
2. Hasenknopf, B.; Lehn, J.-M.; Kneisel, B. O.; Baum, G.; Fenske, D. Angew Chem. Int. Ed. Engl. 1996, 36, 1838.
3. （a）Janini, T. E.; Fattore, J. L.; Mohler, D. L. J. Organomet. Chem. 1999, 578, 260.（b）Ballardini, R.; Balzani, V.; Philp, D.; Ricketts, H. G.; Stoddart, J. F. Angew Chem. Int. Ed. Engl. 1993, 32, 1301.
4. （a）Sauvage, J.-P.; Collin, J.-P.; Chambron, J.-C.; Guillerez, S.; Coudret, C. Chem. Rev. 1994, 94, 993.（b）Balzani, V.; Juris, A.; Venturi, M.; Campagna, S.; Serroni, S. Chem. Rev. 1996, 96, 759.
5. （a）Dong, T.-Y.; Lin, M.-C.; Chiang, Michael, Y.-N.; Wu, J.-Y. Organometallics 2004, 23, 3921.（b）Dong, T.-Y. ; Chen, K.; Lin, M.-C.; Lee, L.-S. Organometallics 2005, 24, 4198.
6. Benniston, A. C.; Grosshenny, V.; Harriman, A.; Ziessel, R. Angew. Chem., Int. Ed. Engl. 1994, 33, 1884.
7. Ziessel, R.; Grosshenny, V.; Hissler, M.; Stroh, C. Inorg. Chem. 2004, 43, 4262.
8. （a）Grosshenny, V.; Ziessel, R. J. Organomet. Chem. 1993, 453, C19.（b）Benniston, A. C.; Grosshenny, V.; Harriman, A.; Ziessel, R. Angewandte Chemie-International Edition 1994, 33, 1884.
9. （a）Grosshenny, V.; Harriman, A.; Ziessel, R. Angewandte Chemie-International Edition 1995, 34, 2705.（b）Grosshenny, V.; Harriman, A.; Ziessel, R. Angew. Chem. Int. Edit. 1995, 34, 1100.
10. 國立中山大學化學系研究生鄭乃元碩士論文.
11. 國立中山大學化學系研究生辜詠傑碩士論文.
12. Dong, T. Y.; Lin, M. C.; Chang, S. W.; Ho, C. C.; Lin, S. F.; Lee, L. J. Organomet. Chem. 2007, 692, 2324.
13. Nishiyama, H.; Shimada, T.; Hirofumi, I.; Sugiyama, H.; Motoyama, Y. Chem. Commun. 1997, 1863.
14. Couchman, S. M.; Dominguez-Vera, J. M.; Jeffery, J. C.; McKee, C. A.; Nevitt, S.; Pohlman, M.; White, C. M.; Ward, M. D. Polyhedron 1998, 17, 3541.
15. Maestri, M.; Armaroli, N.; Balzani, V.; Constable, E. C.; Thompson, A. M. W. C., Inorg. Chem. 1995, 34, 2759.
16. Chen, J. L.; Chi, Y.; Chen, K. Inorg. Chem. 2010, 49, 823.
17. Werner, H.; Zenkert, K. J. Organomet. Chem. 1988, 345, 151.
18. Stephan Steinmann ”Bromination” of organic-chemical practical course in summer semester 2007 of the department of chemistry, university of Basel.
19. （a）Yigit, M. V.; Cooper, C. G. F.; Wang, Y.; Moulton, B.; MacDonald, J. C. J. Chem. Crystallogr. 2006, 36, 371.（b）Wang, Y.; Cooper, C. G. F.; Luisi, B. S.; Moulton, B.; MacDonald, J. C. J. Chem. Crystallogr. 2007, 37, 299.
20. Lainé, P. P.; Bedioui, F.; Loiseau, F.; Chiorboli, C.; Campagna, S. J. Am. Chem. Soc. 2006, 128, 7510.
21. Moghimi, A.; Ranjbar, M.; Aghabozorg, H.; Jalali, F.; Shamsipur, M.; Yap, G. P. A.; Rahbarnoohi, H. J. Mol. Struct. 2002, 605, 133.