Metal Template Synthesis of Novel Interlocked Architectures

Abstract

Molecular knots form spontaneously in natural[1] and synthetic[2] polymers. However, they were not synthesised in small molecule form until the late 1980s. Different templating strategies afforded some of the simplest knots.[3] More complicated knots proved elusive until the circular helicate strategy was presented. This two-step approach involves the formation of a circular arrangement of ligands which is subsequently closed to form a molecular knot. This thesis shows new ways to form mechanical bonds and presents novel molecular knots based on circular helicates. These knots can readily be demetallated. The possibility to control the metals bound to a knot allows for the switching between catalytically active and inactive states. Such systems also allow for the allosteric regulation of catalytic systems.References:[1] L. F. Liu, R. E. Depew, J. C. Wang, J. Mol. Biol. 1976, 106, 439-452.[2] M. Schappacher, A. Deffieux, Angew. Chem. Int. Ed. 2009, 48, 5930-5933.[3] J.-F. Ayme, J. E. Beves, C. J. Campbell, D. A. Leigh, Chem. Soc. Rev. 2013, 42, 1700-1712.

Date of Award	1 Aug 2017
Original language	English
Awarding Institution	The University of Manchester
Supervisor	David Leigh (Supervisor) & Michael Greaney (Supervisor)