| Summary: | <p>This thesis describes the exploitation of non-covalent interactions between components of supramolecular systems, principally rotaxanes and pseudorotaxane assemblies, to enhance the synthesis of mechanically interlocked molecules (MIMs) and for sensing and catalysis applications.</p>
<p><strong>Chapter One</strong> introduces supramolecular chemistry and the non-covalent interactions typically exploited within the field, in particular in the context of anion recognition and sensing. The synthesis of MIM architectures is discussed and their advantages as highly preorganised hosts for the recognition and sensing of charged guests, and in catalysis applications, is discussed through examples from the literature.</p>
<p><strong>Chapter Two</strong> describes the high yielding synthesis of a series of Zn(II) metalloporphyrin [2]- and [3]-rotaxanes. The inter-component macrocycle pyridyl⋯Zn(II) metalloporphyrin axle interaction is investigated by variable temperature 1H NMR spectroscopy and by rotaxane transmetallation studies. The binding of neutral or anionic competing guest ligands, and the resultant change in the metalloporphyrin optical spectra, is investigated and a [2]rotaxane congener with a heteroditopic macrocycle synthesised to investigate the effects of rotaxane co-conformational dynamism on ion-pair binding.</p>
<p><strong>Chapter Three</strong> describes the use of pillar[5]arene host-guest chemistry to form pseudorotaxanes as a potential route to higher order [3]- or [4]-rotaxanes and for facile stoppering by a phosphaalkyne-azide click reaction to form organometallic-containing [2]rotaxanes. The effect of the mechanical bond to stabilise air- and moisture-sensitive organometallic species is investigated. Furthermore, the ability of a hydrophobic pillar[5]arene host system functionalised with halogen bonding motifs and an optical reporter group to sense neutral and anionic environmental pollutants is explored.</p>
<p><strong>Chapter Four</strong> presents a series of transition metal salen complexes in [2]rotaxane MIM and non-interlocked frameworks, and investigates the potential of supramolecular non-covalent interactions to catalyse the synthesis of sustainable polyester and polycarbonate polymers.</p>
<p><strong>Chapter Five</strong> presents the main conclusions of this thesis.</p>
<p><strong>Chapter Six</strong> details the experimental procedures used in the work in this thesis and presents the full characterisation of all novel compounds.</p>
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