The synthesis and separation properties of organic cage compounds

Kewley, Adam
The synthesis and separation properties of organic cage compounds. PhD thesis, University of Liverpool.

[img] Text
KewleyAda_Nov2014_2010659.pdf - Unspecified
Available under License Creative Commons Attribution.

Download (12MB)


Microporous materials play an important role in a variety of industrial and domestic applications. While a diverse range of microporous materials have been identified, this thesis focuses on porous organic cages (POCs) because they have received much attention as synthetically tunable, solution processable, microporous materials. After introducing the latest developments in POC synthesis and the general application of microporous materials as selective sorbents, this thesis presents three developments in organic cage chemistry: a high-throughput workflow for the discovery of POCs, which yielded a novel organic cage compound; the measurement of selective adsorption by POCs, wherein the first instance of chiral selectivity by a POC was recorded; and the first instance of applying POCs as stationary phases for gas chromatography, which produced columns that separate racemic mixtures, alkylaromatic isomers, and alkane isomers. Chapter 2, discovering novel organic cages, presents attempts to use high-throughput and in-silico techniques to accelerate the discovery of novel organic cages. These methods were utilised to isolate a novel organic cage, CCX-S, which is characterised and discussed. Chapter 3, organic cages as selective sorbents, presents the development of approaches for measuring selective adsorption. These methods were used to identify the first reported instance of enantioselective adsorption by an organic cage. Further measurements to explain this separation behavior are also presented. Chapter 4, chromatographic separations with organic cages, presents one method of practically leveraging the presented separation behavior. In Chapter 4, the coating of capillary columns with CC3 is presented. These columns were used to successfully perform gas chromatographic separations, the first recorded instance of using a POC to do so. The columns were further improved by modifying the coating method and using prefabricated CC3 nanoparticles. This modification enabled difficult separations to be performed using the column; for example, the separation of hexane’s five isomers.

Item Type: Thesis (PhD)
Additional Information: Date: 2014-11 (completed)
Uncontrolled Keywords: Porous materials, organic cages, high-throughput automation, gas chromatography, GC, capillary columns, imine condensation, selective adsorption, microporous
Subjects: ?? Q1 ??
?? QD ??
?? TP ??
Depositing User: Symplectic Admin
Date Deposited: 04 Aug 2015 10:40
Last Modified: 17 Dec 2022 01:27
DOI: 10.17638/02010659
Publisher's Statement : A fun research project with an excellent team. Researching organic cages under the supervision of Andy Cooper was an enlightening experience that taught me how to make new compounds, analyze interesting behavior, and practically apply academic research to a commercially lucrative piece of technology. In writing this thesis, I have tried to summarize all the major findings of the project in the fewest pages possible. Don't let its brevity fool you though. This thesis contains a wide variety of new approaches I hope will be useful to the next generation of porous materials researchers.