Construction of Metal-Organic Cages with Bimetallic Motifs and Self-Assembly of a Molecular Knot

This thesis can be divided into two parts. These two sections differ not only in terms of the molecular structures they are concerned with, but also in their general approach to designing new, complex metal-organic structures. The first portion of the thesis focuses on the self-assembly of metal-organic polyhedra built around bimetallic complexes. The components were specifically chosen to increase the chances of serendipitous and unexpected results coming about. A series of such structures are presented; a dicopper(I)- and disilver(I)-based octahedra, hetero-bimetallic cadmium(II)-copper(I) tetrahedral and a family of disilver(I)-based trigonal prism. Each of these structures are constructed around previously unreported coordination motifs. Nearly all of the results in this part of the thesis were arrived at through serendipity. The second part takes an entirely different approach to the design of complex architectures. While it builds upon serendipitous results generate in the Nitschke group several years prior, it is a hypothesis-driven endeavour. A topologically complex molecular knot with eight crossings is reported. The ability of enantiopure subcomponents to affect the handedness of the knot is also investigated, with this work ultimately aiming toward the enantioselective synthesis of a purely topologically chiral molecules. The thesis concludes with a chapter detailing conclusions drawn from this body of results and future work which follows from it on the synthesis of even more topologically complex structures.

Level dc:type.qualificationlevel

Doctoral

Grantor dc:publisher.institution

University of Cambridge

Year dc:date.issued

2020

Author dc:creator

• Carpenter, John

Advisor dc:contributor.advisor

• Nitschke, Jonathan

• Chemistry
• Supramolecular

Licence

• https://apollo8-f-pro.lib.cam.ac.uk/bitstreams/fc3e03b8-766d-4dd3-baf3-8cbc413d3eaf/download
• https://www.rioxx.net/licenses/all-rights-reserved/

Language dc:language

eng

DOI dc:identifier.doi

https://doi.org/10.17863/CAM.62361

OAI identifier oai:identifier

oai:www.repository.cam.ac.uk:1810/315255