Penty, Samuel E. 
ORCID: 0000-0003-4554-0855
(2025).
Bis-perylene diimide macrocycles for chiroptical materials.
University of Birmingham.
Ph.D.
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Abstract
This thesis aims to explore the intramolecular and intermolecular interactions between chiral core-twisted PDIs using a novel bis-PDI macrocyclic scaffold (nicknamed the “Pink Box” due to its colour in solution), with a view towards applications as organic chiroptical materials.
Chapter 1 provides an overview of chiroptical activity and of perylene diimides (PDIs), with an emphasis on their supramolecular self-assembly and on chiral bis-PDI macrocycles.
Chapter 2 outlines the development of the Pink Box macrocyclic scaffold, as well as the characterisation of its intramolecular homochiral PDI-PDI dimer using a range of experimental
techniques.
Chapter 3 established a strategy for making the Pink Box macrocycle chirally locked by varying the imide group on the PDIs to prevent an “intramolecular somersault”. With stable enantiomers in hand, the aggregation behaviour of enantiopure vs racemic macrocycle samples is studied by UV-vis spectroscopy and X-ray crystallography. It is found that the intramolecular PDI-PDI dimer within the macrocycle is always homochiral and H-type, while intermolecular PDI-PDI contacts are heterochiral and slip-stacked.
Chapter 4 provides a fundamental understanding of the chiral conformations of “Pink Box” type macrocycles to unlock further potential as efficacious chiroptical materials. A 3rd generation Pink Box macrocycle is developed in which the homochiral stereoisomers can populate two different chiral conformations upon changing the solvent, leading to inversion of the CD spectrum (chiroptical switching). Additionally, a stable heterochiral diastereomer is isolated and shown to exhibit a “slipped-stack” J-type dimer.
Chapter 5 describes the synthesis and characterisation of a series of Pink Box-type macrocycles with alternative linkers, to understand the impact of linker length and rigidity on the interaction between the PDI units in a bis-PDI macrocycle. Guest binding studies are also performed.
Chapter 6 provides a summary of the major conclusions from the research described in this thesis.
Experimental details and methodologies are provided at the end of each research chapter.
Appendix A provides details of the computational studies carried out by Prof Martijn Zwijnenburg to complement the research presented in this thesis.
| Type of Work: | Thesis (Doctorates > Ph.D.) | |||||||||
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| Award Type: | Doctorates > Ph.D. | |||||||||
| Supervisor(s): |
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| Licence: | Creative Commons: Attribution-Noncommercial 4.0 | |||||||||
| College/Faculty: | Colleges > College of Engineering & Physical Sciences | |||||||||
| School or Department: | School of Chemistry | |||||||||
| Funders: | None/not applicable | |||||||||
| Subjects: | Q Science > QD Chemistry | |||||||||
| URI: | http://etheses.bham.ac.uk/id/eprint/15668 |
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