Date of Award

Summer 7-18-2014

Document Type

Thesis

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry & Biochemistry

First Advisor

Wei Zhang

Second Advisor

David Walba

Third Advisor

Cortlandt Pierpont

Abstract

Shape persistent 2-D macrocycles constructed via alkyne metathesis have been well explored in the past decade. However, 3-D Covalent Organic Polyhedrons (COPs) synthesized through alkyne metathesis have been rarely studied. The objective of the work described in this thesis is to explore the efficient assembly of 3-D shape-persistent covalent organic polyhedrons through dynamic alkyne metathesis and study the relationship of the COP structures and the geometry of their building blocks. The applications COPs in host-guest chemistry, specifically the interactions with fullerenes will be discussed.

In Chapter 1, an overview of the current advances in alkyne metathesis reactions and their application in organic materials development, including design and synthesis of novel polymers, shape-persistent 2-D macrocycles, 3-D molecular cages and porous frameworks.

In Chapter 2, the design and synthesis of a tetrameric COP with an unexpected D2h symmetry through one-step alkyne metathesis from a C3 symmetrical monomer is discussed. The COP structure was confirmed by the signal crystal X-ray diffraction. This COP exhibits high binding affinity with C70 over C60 (KC70/KC60 > 1000).

In Chapter 3, the synthesis of a dumbbell-shape tetrameric COP through alkyne metathesis is discussed. The formation of the tetrameric structure instead of entropically-favored dimeric one is investigated through computer modelling study. The cage also serves as a host for fullerenes.

In Chapter 4, the relationship between cage structures and the geometry of monomers in the dynamic assembly process is discussed. A dimeric cage and its interlocked cages were obtained in one-pot alkyne metathesis starting from an extend C3 symmetry monomer.

In Chapter 5, the design and synthesis of a series of pyrene based COPs are described. These COPs exhibit strong fluorescence and significant binding affinity with fullerenes. They can be transferred into cells, which have potential applications in diagnosis. A water soluble pyrene cage was also synthesized and its biological property study is undergoing.

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Chemistry Commons

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