Rational design and applications of chiral supramolecular systems.

摘要

The design of functional supramolecular assemblies has received intense interest from synthetic and materials chemists. Many fascinating supramolecular architectures have been synthesized and some of them have found applications in enantiomeric fluorescence sensing, catalysis, separation processes. Motivated by many successful studies, we are interested in the design of chiral cyclic nanoscopic architectures. In this dissertation, rational design and characterization of chiral supramolecular systems including discrete polygons and extended metal-organic frameworks are described. The interesting trimer-tetramer equilibrium via self-assembly, the application of the highly emissive molecular squares, and the interesting aggregation behavior of shape-persistent macrocycles are also detailed in this dissertation.; Chapter 1 gives a brief overview of the latest developments in the synthesis of macrocycles and more importantly, their applications in many fields.; Chapter 2 presents the synthesis and characterization of Pt (II) diimine based chiral metallcycles and their applications in OLED devices.; Chapter 3 discusses the design and synthesis of chiral metallocycles based on bipyridine ligands and cis-Pt(PEt3) 2 metallocorners. Their trimer-tetramer equilibrium behaviors were studied by DOSY-NMR Spectroscopy.; Chapter 4 investigates the synthesis of metal-free macrocycles via self-assembly and directed-assembly method based on chiral bis(alkynyl) linkers at the 3,3'- and 6,6'- positions. These shape-persistent macrocycles were characterized by a variety of spectroscopic technique and single crystal X-ray crystallography. Aggregation studies are also discussed.; Appendix details the synthesis and characterization of homochiral metal-organic frameworks based on 4,4'-bipyridine-BINOL bridging ligands.