Design, synthesis, and applications of chiral nanoscopic and mesoscopic supramolecular architectures: Metallodendrimers and metallocycles.

摘要

The objective of this thesis research is to design and synthesize chiral nanoscopic and mesoscopic supramolecular architectures, including metallodendrimers and metallocycles. Their interesting optical properties and applications in asymmetric catalysis were explored. The interesting luminescence properties of metallodendrimers are described. The efficient self-assembly approach was used to construct chiral molecular polygons ranging from triangle and octagons, while the stepwise directed-assembly approach was used to synthesize much larger mesoscopic metallocycles with cavities of up to 22 nm.; Chapter 1 gives an overview of metallodendrimers and metallocycles. The general synthetic strategies are illustrated by some examples of chiral metallodendrimers and metallocycles.; Chapter 2 presents the synthesis and characterization of ruthenium-terpyridine based chiral metallodendrimers and their interesting generation dependent luminescence properties.; Chapter 3 discusses the design and synthesis of chiral dimeric metallocyclophanes based on chiral bis(alkynyl) linkers and cis-Pt(PEt3)2 metallocorners and their applications in asymmetric catalysis.; Chapter 4 demonstrates the self-assembly of chiral nanoscopic molecular polygons ranging from triangle to octagon by using 2,2'-diacetoxy-1,1 '-binaphthyl-6,6'-bis(ethyne) as a bridging ligand and a trans-Pt(PEt3)2 group as the metal-connecting point.; Chapter 5 describes the expeditious stepwise directed-assembly of chiral mesoscopic metallocycles based on 2,2'-diacetoxy-1,1 '-binaphthyl-6,6'-bis(ethyne) bridging ligands and trans-Pt(PEt3)2 metal-connectors. Characterization of mesoscopic metallocycles by size exclusion chromatography (SEC) and diffusion-ordered NMR spectroscopy is also described.; Chapter 6 discusses the expeditious stepwise directed-assembly of chiral mesoscopic metallocycles based on 2'-diacetoxy-1,1 '-binaphthyl-3,3'-bis(ethyne) bridging ligands and trans-Pt(PEt3)2 metal-connectors.