Date of Award

Spring 1-1-2016

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry & Biochemistry

First Advisor

Wei Zhang

Second Advisor

Douglas L. Gin

Third Advisor

Hai Long

Fourth Advisor

Richard D. Noble

Fifth Advisor

Hang Yin

Abstract

The objectives of this thesis are to utilize dynamic covalent chemistry (DCvC) to prepare organic macrocycles and cages, construct subsequent complex architectures through self-assembly, and investigate the properties and applications of these compounds for supramolecular chemistry, transmembrane channels, gas adsorption, etc. Traditionally, organic macrocycles and cages are prepared via irreversible bond formation reactions, which usually require multi-step syntheses and tremendous synthetic efforts, result in low overall yields. DCvC, which enables reversible bond breaking/forming, and allows the most thermodynamically stable product to form predominantly at equilibrium, has largely facilitated the preparation of organic macrocycles and cages.

In this thesis, Chapter 1 reviews shape-persistent macrocycles prepared through DCvC, including sections on a variety of dynamic covalent reactions (DCRs) such as alkyne metathesis, imine metathesis, olefin metathesis, boronate ester formation, and orthogonal DCRs. Chapter 2 shows syntheses of phenylene vinylene macrocycles (through olefin metathesis) and phenylene ethynylene macrocycles (through alkyne metathesis), their aggregation behavior, and their ability to function as transmembrane transporters. Chapter 3 presents the syntheses of cyclic porphyrin trimers through alkyne metathesis, their host–guest chemistry with fullerenes and pyridine-based ligands, their guest exchange and host exchange self-sorting behavior, and their ability to function as ligand-gated transmembrane ion channels. Chapter 4 describes the design principles, syntheses, and application of a series of porphyrin-based cages and non-porphyrinic cages (through olefin metathesis or alkyne metathesis). Chapter 5 displays efforts towards the construction of complex architectures from organic cages through self-assembly or covalent-linkage, plus the gas adsorption performance of certain structures.

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