利用官能化三配向三聯三吡啶配位基架構功能性籠狀超分子之研究

Self-Assembly of Functional Metallo-Supramolecular Cages Using Tritopic Terpyridine-Based Ligands

許庭瑋(Ting-Wei Hsu)

指導教授 ： 詹益慈

國立臺灣大學/理學院/化學研究所/碩士(2015年)

https://doi.org/10.6342/NTU.2015.10787

摘要

在超分子領域中，許多團隊致力於架構立體的籠狀超分子；現今已有各式各樣的三維高對稱結構被創造及報導。本實驗中，我們成功展示籠狀超分子外修飾的可能性；透過合成一系列帶有不同官能基團的三配向三聯三吡啶配位基並與金屬離子錯合形成立方體的超分子；含有不同基團的立方超分子表現出相異的性質，例如溶解度；透過氫核磁共振、電灑式質譜及電子顯微鏡等技術來鑑定及觀察其自組裝後的結果和行為。除此，我們亦利用連接不同位點的聯三吡啶，形成向內彎曲的三聯三吡啶配位基結構並與金屬離子錯合形成較小的籠狀超分子；藉由連接位點的改變微調配基幾何結構，更多的三維超分子可以簡單地被建構。
現今以噻吩及碳球衍生物為主動層之有機太陽能電池具有穩定性不佳的問題，其中有部分原因為小分子的碳球衍生物隨時間產生大規模聚集進而造成主動層間嚴重的巨觀相分離；因此，我們將富勒烯引入至三配向三聯三吡啶配位基上，透過自組裝形成帶有八個富勒烯的立方超分子，並作為交聯劑降低碳球衍生物在主動層的聚集速度，成功改善有機太陽能電池的穩定性。

關鍵字

聯三吡啶 ； 籠狀超分子 ； 富勒烯 ； 有機太陽能電池

並列摘要

In supramolecular chemistry, constructing a well-defined three-dimensional cage has attracted more and more attention. Herein, we explore the possibility of exterior functionalization for the self-assembled cages. A series of tritopic terpyridine-based ligands with various exterior functionalities was used to construct metallo-supramolecular cages. To investigate the self-assembly behavior of the predesigned tritopic ligand system, ligands with simple hydroxyl and alkyl substituents were synthesized and complexed with Cd(II) and Zn(II) ions to give supramolecular cubic cages that were well characterized by 1H-NMR, ESI-MS, and electron microscopes. Besides, changing connected positions between the terpyridine moieties and the central core to generate a bent version of the tritopic ligand was successfully used for constructing a smaller supramolecular structure, demonstrating a simple method to build variant metallo-supramolecular structures.
To date, the polymer solar cells (PSCs) with P3HT and PCBM as an active layer suffer from a severe lifetime problem, which is partly caused by the macrophase separation from the aggregation of PCBM with time. Based on our new findings, the tritopic terpyridine-based ligand decorated with pendant fullerene groups was successfully synthesized and self-assembled into a functional metallocage via coordination. In addition, the fullerene-functionalized cage was used as a supramolecular crosslinker to alleviate the macrophase aggregation caused by the migration of the C60 acceptor, which significantly improved the stability of organic photovoltaics.

並列關鍵字

terpyridine ； metallo-supramolecular cage ； exo-funtionalization ； fullerene ； solar cell

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