- 學位論文
利用含多聯三吡啶配位基以自組裝方法架構立體籠狀超分子之研究
Self-assembly of 3D Metallo-Supramolecular Cages
摘要
近年來超分子研究領域蓬勃發展，其中，利用金屬與配體間的配位作用力來建構超分子化合物更是熱門的研究方向。此類非共價鍵結具有豐富的應用性，可以應用於表面修飾，分子探針以及立體結構上的合成。 由於自組裝的過程由熱力學主導，我們無法分步控制其組裝過程，因此，在利用金屬與配體的作用力來建造立體結構時，最主要的關鍵是在於配基的幾何形狀以及剛性。利用設計好的配基形狀來驅使自組裝後會形成預期的產物。再者，我們發展出具有配位選擇性的聯三吡啶與金屬離子配位對。在建構超分子結構時引入具有選擇性的配位對可以大大降低組裝上的困難以及縮短合成的路徑，尤其是在具有多種組成配基與金屬離子的情況下。 在此研究中我們成功地建構出四種超分子結構，分別來自於以四配向與五配向多聯三吡啶配位基與金屬的自組裝，並混入具有60度與120度夾角的具選擇性雙聯三吡啶配基，在多組成下形成單一的超分子結構。本論文將仔細探討其配基與超分子結構的合成與鑑定，並探討其應用性。
並列摘要
Supramolecular chemistry has received tremendous attention over the past few decades. Among them, coordination-driven self-assembly is one of the most important processes utilized in supramolecular chemistry because of the prolific applications in surface modification, molecular probes, architecture construction, etc. For preparation of supramolecular architectures by coordination-driven self-assembly, the geometry of building blocks plays an important role in achieving the desired self-assembled product. In this research, well-defined terpyridine-based ligands are used to build up 3D supramolecular cages. In addition, we recently developed a complementary ligand pair that is able to spontaneously afford a heteroleptic complex in the presence of metal ions under ambient conditions. The presented approach provides facile access to construction a variety of polygons and polyhedrons. Four kinds of novel metallo-cages were successfully constructed by using the multi-topic terpyridine ligands along with the modified 60o- and 120o-bent bis(terpyridine) ligands. The structural characterization was carefully established by NMR, ESI-MS, ESI-TWIM-MS, AFM, and TEM experiments.
參考文獻
延伸閱讀
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