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Title: Palladium(II) templated syntheses of interlocked architectures
Author: Fuller, Anne-Marie L.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2007
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Herein, the application of palladium(II) combined with a “3+1” pyridine-2,6-dicarboxamido and pyridine heteroligand set is described. While it may seem reasonable to expect that a two-dimensional coordination geometry would not be well suited for the synthesis of inherently three-dimensional interlocked architectures, the reverse has been shown to been true. Indeed, it has proven itself to be a very proficient and versatile template motif, exemplified by the syntheses of various multi-component architectures. Initially, this template was applied to the synthesis of the first [2]rotaxane whose formation was directed by a metal ion with a square planar geometrical preference. Importantly, the heteroleptic nature of the motif enabled a clipping strategy, which would not have been possible using a homoleptic system; this particular trait being essential for the synthesis of more intricate structures. Subsequently this template was used for the assembly of a [2]catenane together with two isomers of this interlocked structure: a single tetradentate macrocycle which adopted a “figure of eight” conformation encapsulating the metal, and a complex in which two macrocycles of the catenane are not interlocked. The three isomers were selectively formed depending on how the building blocks were assembled and cyclised. The efficacy of this palladium(II) template was further demonstrated by its application to the construction of increasingly complex architectures such as multi-ring rotaxanes. It provided fundamental control over the addition to a thread of individual macrocycles, which could be sequentially clipped-on using only one template site, by the iteration of three simple steps – complexation, macrocyclisation and demetalation. This impressive control has also allowed the syntheses of a unique pair of [3]rotaxanes that exhibit sequence isomerism through the use of two different macrocycles.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available