Self-Assembly of 3D Metallo-Supramolecular Cages from Terpyridine-Based Ligands with Crown Ethers as Central Units

• Main Authors: Yun-Chi Wang, 王允齊
• Other Authors: Yi-Tsu Chan
• Format: Others
• Language: en_US
• Published: 2015
• Online Access: http://ndltd.ncl.edu.tw/handle/49257698248297914021

碩士 === 國立臺灣大學 === 化學研究所 === 104 === Molecular self-assembly using metal-ligand coordinative interaction has drawn much attention in recent years. Utilizing non-covalent interactions provides a facile way to construct large and complicated 2D/3D structures in contrast with the conventional organic chemistry. Moreover, incorporation of orthogonal host-guest and metal-coordination interactions into supramolecular structures will enhance their structural complexity and impart additional functions. In this research, we designed and synthesized a series of metallo-supramolecular cages possessing multiple <tpy-MII-tpy> (tpy = terpyridine) connections and ion–dipole interaction sites (i.e., crown ethers), which functioned orthogonally to each other. It was found that a decrease in the size of crown ethers leaded to a decrease in the flexibility, and thus various thermodynamic products were formed. To further study these metallo-supramolecular cages, we investigated the interactions between the crown ethers and the predesigned secondary ammonium ions. The 1:1 inclusion complex formed by the cage assembly and the multivalent ammonium salt was successfully achieved in MeCN and further characterized by NMR spectroscopy and ESI mass spectrometry. The formation of a metallo-supramolecular rotaxane based on the inclusion compound was explored as well.