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Catalysis and host-guest chemistry of M8L12 self-assembled cages
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Mozaceanu, Cristina (2022) Catalysis and host-guest chemistry of M8L12 self-assembled cages. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3884354
Abstract
Chapter 1 – The first chapter introduces supramolecular chemistry, metal-organic cages, and supramolecular mass spectrometry. Finally, the aims of this work are stated.
Chapter 2 – The second chapter covers the synthesis and characterisation of a family of M8L12 cages. Additionally, destructive and non-destructive methods for the recovery of these cages or their contained ligands have been investigated. The addition of EDTA as a complexing reagent to mixtures of guests and M8L12 cages was the most successful and sustainable method for recovering the ligands. It was shown that the cage could be successfully re-synthesised.
Chapter 3 – This chapter introduces binding studies of three isomeric guests of different polarities (1,2-, 1,3- and 1,4-dicyanobenzene) inside two M8L12 cages in D2O/DMSO-d6 (98:2) and CD2Cl2 via NMR spectroscopy. In both solvents, the guest binding strength correlates with the guest polarity, the binding in water being stronger due to additional hydrophobic contributions. A can’t Hoff analysis in water emphasised that the differences in the guest binding energies arise from the entropy of binding, due to differences in the guest desolation across the series.
Chapter 4 – In this chapter, the properties of a M8L12 cage in the gas phase are presented. By utilising electrospray mass spectrometry, a M8L12 cage and its complexes were successfully ionised and their stability studied. Ion mobility spectrometry revealed the guest binding properties for complexes containing cycloundecanone (CUD), 4-methylcoumarin (MC), and 7-amino-4-methylcoumarin (MAC) as guests. CUD binds inside the cage cavity forming a 1:1 complex. For MC and MAC, the amino group influences the formation of cage/coumarin complexes: i) MC formed only 1:1 and 1:2 species, whilst with MAC, up to 1:8 stoichiometries were obtained. ii) ion mobility data indicated that the MAC and MC molecules were externally bound.
Chapter 5 – The final chapter presents the aldol self-condensation of 1,3-indandione catalysed by a M8L12 cage in water. In the presence of the cage, the reaction undergoes slowly at weak acidic conditions, but without the cage, no reaction is observed. By inhibiting the cavity, the reaction was revealed to occur at the cage surface.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Organometallic compounds, Metal-organic frameworks, Coordination compounds, Supramolecular chemistry, Catalysis, Ligands (Biochemistry), Mass spectrometry | ||||
Official Date: | September 2022 | ||||
Dates: |
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Institution: | University of Warwick | ||||
Theses Department: | Department of Chemistry | ||||
Thesis Type: | PhD | ||||
Publication Status: | Unpublished | ||||
Supervisor(s)/Advisor: | Ward, Michael D. | ||||
Sponsors: | European Union | ||||
Format of File: | |||||
Extent: | xii, 186 pages : illustrations | ||||
Language: | eng |
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