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Title: Subcomponent self-assembly : from topological complexity to dynamic systems
Author: Campbell, V. E.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2010
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This thesis initially (Chapter 1) reviews some of the background literature for constitutional dynamic chemistry (supramolecular and dynamic covalent chemistry), templated self-assembly, subcomponent self-assembly, oligoamide foldamers, and systems chemistry. The motivation in bringing these areas together was the construction of both topologically complex architectures (such as helicates, macrocycles, catenanes, knots and large proteomorphous entities) and complex dynamic self-assembling systems. Chapter 2 describes the synthesis of homometallic and heterometallic structures (helicates and a pincer-like complex) via subcomponent self-assembly. These helicates readily participated in a dynamic system of transformations where the limited addition of a building block imposed the subcomponents to preferentially assemble into well-defined predicted structures. In Chapter 3, the construction of an atypical dicopper(I) helical macrocycle and catenane were shown. This macrocycle participated in a series of imine exchange reactions mediated by electronic effects, entropic effects and the coordinative preferences of copper(I) ions. The thermodynamic stability of this macrocycle was extrapolated through van’t Hoff analysis of an imine exchange reaction. Chapter 4 describes the synthesis of large proteomorphous objects. Amine-functionalized aromatic oligoamide foldamers were employed as building blocks in subcomponent self-assembly reactions. It was possible to assemble helices at angles of 90° and 180°, and to assemble up to four helices around copper(I) ions, synthesising large tertiary structures whose molecular weights approaches those of proteins. Chapter 5 outlines some of latest preliminary results towards more complex architectures and systems.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available