以POSS為核心單元之單分子四重夾設計及其主客體端點修飾

Design of POSS-Based Molecular Quaternary Clips and End-functionalization of Host-Guest Complexes

彭偉承(Wei-Cheng Peng)

指導教授 ： 王建隆

國立交通大學/理學院/應用化學系所/碩士(2019年)

摘要

分子夾在主客化學領域中因溶解度佳，容易修飾官能基以及相對於傳統環形主體有更彈性的空間去夾取客體，使其逐漸發展起來；但是目前的分子夾以單夾或單分子雙夾為主，超過雙夾以上的分子夾尚未被報導過，使得分子夾的多樣性及功能性受到了限制。在本篇論文中，成功以POSS為核心單元合成了Q clip單分子四重夾。POSS被認為是最小的氧化矽奈米粒子，其粒徑約0.5-0.8奈米。在POSS核心的八個頂點上修飾上不同的共軛取代基，可形成三維共軛巨分子。我們利用POSS核心所建立起的空間以及其設計頂點修飾多電子的芘 (pyrene)為官能基，藉由電荷轉移作用力可以夾取4當量的萘二醯亞胺衍生物(Naphthalene diimide, NDI)Hex-NDI；且Q clip在夾取Hex-NDI形成主客體複合物的過程中，能夠收斂芘(pyrene)的官能基手臂，使原本為不定形態(amorphous)的Q clip能形成柱狀相，並形成層列型液晶相。另外，Q clip對於官能化修飾的萘二醯亞胺衍生物Py-NDI, Amine-NDI, OH-NDI同樣具有選擇性，能夠夾取4當量的客體分子並形成柱狀相；最後，我們可以利用官能化的NDI，並經由添加劑的加入，對主客體奈米柱的端點進行官能化修飾，修飾上不同的分子間作用力，為分子夾添增了功能性以及多樣性。

關鍵字

主客化學 ； 分子夾 ； 單分子四重夾 ； 多面體聚矽氧烷衍生物 ； 萘二醯亞胺衍生物

並列摘要

Molecular clips are developing in host-guest chemistry because of good solubility, easier to functionalized and more flexible space to clamp guest than traditional macrocycles. The number of clips in molecular clips which is bigger than 2 has never been reported, and the versatility and functionality of molecular clips has been restricted. In this thesis, we use POSS nanoparticle as unit core to synthesize Q clip, which is molecular quaternary clip. POSS is considered to be the smallest silicon nanoparticle, and size is 0.5-0.8 nm. Functionalize different conjugate groups onto the eight vertices of POSS and three dimension giant molecule would be formed. We use the space built up by POSS and functionalize electron-rich pyrene onto POSS. Q clip can clamp 4 equivalent of Hex-NDI by charge transfer interaction. In the formation of host-guest complex, Q clip would be conformation change from amorphous to rod-like by the elongation of functional groups in Q clip. However, Q clip can clamp 4 equivalent of functionalized NDI derivatives such as Py-NDI, Amine-NDI and OH-NDI. Last, we can functionalize the end-side of host-guest nanorod by noncovalent interactions between functionalized NDI and additive. We have successfully pioneer the functionality and versatility of molecular clips.

並列關鍵字

Host-Guest Chemistry ； Molecular Clips ； Quaternary Molecular Clips ； POSS derivatives ； NDI derivatives

參考文獻

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