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標題: | 多組份星狀超分子之自組裝行為的探討 Multicomponent Self-Assembly of Star-Shaped Metallo-Supramolecules |
作者: | "Shi-Cheng, Wang" 王士誠 |
指導教授: | 詹益慈(Yi-Tsu, Chan) |
關鍵字: | 聯三?啶,多組份自組裝,互補性鍵結,多價性鍵結,星狀超分子, terpyridine,multicomponent self-assembly,complementary binding,multivalency,star-shaped supramolecule, |
出版年 : | 2018 |
學位: | 碩士 |
摘要: | 在金屬配位驅動自組裝領域中,含有2,2′:6′,2′′-聯三吡啶官能基的配位體常用於架構金屬超分子。多組份的系統中,為了消除可能的動力學副產物,精密的配位體設計是有急迫需要的。在這份研究中,我們的自組裝方法引入了多價性鍵結以及互補性鍵結。前者是藉由協同效應來增加結構穩定性,後者則透過修飾巨大體積的官能基在聯三吡啶的6,6′位置上,達到如同雙股螺旋鹼基配位對相似的自分類選擇性。
在本論文的第一個研究方法中,我們融合了多價性鍵結以及互補性鍵結,創造了一個含有八配向多聯三吡啶、具有巨大體積官能基修飾的聯三吡啶以及金屬離子的三組份系統。此系統將用於創造六芒星狀的金屬超分子以及探討多價性鍵結和互補性鍵結之間的機制。 在本論文的第二個研究方法中,我們根據形狀的對稱性,創造了在聯三吡啶化學史上第一個四組份的自組裝系統。此方法透過將結構切成簡單三種重複單元,簡化了合成的難度,並在其中兩種單元上加入了互補性鍵結防止其他結構的產生。此外,受益於結構當中不同的鍵結強度,雙金屬超分子結構可以透過換金屬方式來達成。 In the coordination-driven self-assembly field, 2,2':6',2'-terpyridine (tpy)-based ligands offer facile access to construction of metallo-supramolecules. In a multicomponent system, delicate ligand designs are needed to eliminate formation of kinetically trapped byproducts. Herein, we introduce multivalency and complementary ligand concepts into our self-assembly strategy. The former indicates the importance of cooperativity and the latter shows a self-selective coordination by incorporating bulky groups at terpyridyl 6,6'-positions. The first method for creation of a six-pointed star was based on multivalency and complementary ligand pairing, leading to a three-component self-assembly system including an octakisterpyridine, a 60°-bent functionalized bisterpyridine, and metal ions. In addition, several structures were designed to discuss the self-assembly mechanism. Being the first example in the tpy chemistry, a four-component system was designed to achieve a six-pointed star based on the ligand geometry. By dividing the structure into repeatable units, three different ligands were created, two of which were modified with bulky groups. This self-assembly process gave rise to a six-pointed star in quantitative yield. The presented metallo-supramolecular structures were fully characterized by 1H NMR, COSY, ROESY, DOSY, ESI-MS and TWIM-MS analyses. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/77522 |
DOI: | 10.6342/NTU201802297 |
全文授權: | 未授權 |
顯示於系所單位: | 化學系 |
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ntu-107-R05223129-1.pdf 目前未授權公開取用 | 18.73 MB | Adobe PDF |
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