Date of Award

1-1-2023

Language

English

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

College/School/Department

Department of Chemistry

Content Description

1 online resource (vii, 209 pages) : illustrations (some color)

Dissertation/Thesis Chair

Jeremy Feldblyum

Committee Members

Qiang Zhang, Alan Chen, Michael Yeung

Keywords

ferrocene metallopolymers, hitorins, polymers of intrinsic micoporosity, porous materials, total synthesis, Organometallic polymers, Polymerization, Porosity

Subject Categories

Chemistry

Abstract

This work focuses on two research directions: the total synthesis of natural products hitorins A and B and the synthesis of porous metallopolymers/ metallooligomers and study of their properties. Nature has a good understanding and makes good use of cascade reactions to generate complex natural structures. The synthesis of hitorins A and B employed a radical cascade starting from a rare intermolecular alkoxy radical-olefin coupling reaction in our biomimetic synthetic strategy. A radical clock experiment was designed to reveal the mechanism for the key alkoxy radical-olefin coupling cascade. Microporous materials have many applications in diverse areas including gas separation, electronic devices, and energy storage. In this work, a series of porous, linear (non-network) metallopolymers termed “metallopolymers of intrinsic microporosity” (MPIMs) were discovered. These polymers exhibit intrinsic microporosity stemming from backbone contortion introduced by the polymers’ main-chain metal ions. Spectroscopic analysis provided evidence for mixed valency between neighboring ferrocenyl units. However, direct measurement of electronic characteristics was hindered by the poor solubility of this class of MPIMs, although copolymers with pendant groups affixed to the phenyldiacetylene units were synthesized to simultaneously maintain porosity and introduce adequate solubility. Ferrocene-containing metalloligomers were obtained with precise degrees of polymerization, which are expected to have even better solubility compared to the analogous MPIMs. Further exploration of porosity provided a better understanding of factors leading to porosity by comparing monomers, short oligomers, long oligomers, and polymers between gas sorption analysis and computation. More exploration of optical and electronic properties is ongoing.

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