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

• Main Authors: Ting-Wei Hsu, 許庭瑋
• Other Authors: Yi-Tsu Chan
• Format: Others
• Language: en_US
• Published: 2015
• Online Access: http://ndltd.ncl.edu.tw/handle/56541699435939278943

碩士 === 國立臺灣大學 === 化學研究所 === 104 === 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.