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The anion-intercalation chemistries of graphite have the potential to construct batteries with promising energy and power breakthroughs. Here, we report the use of an ultrathin, positively charged two-dimensional poly(pyridinium salt) membrane (C2DP) as the graphite electrode skin to overcome the critical durability problem. Large-area C2DP enables the conformal coating on the graphite electrode, remarkably alleviating the electrolyte. Meanwhile, the dense face-on oriented single crystals with ultrathin thickness and cationic backbones allow C2DP with high anion-transport capability and selectivity. Such desirable anion-transport properties of C2DP prevent the cation/solvent co-intercalation into the graphite electrode and suppress the consequent structure collapse. An impressive PF6−-intercalation durability is demonstrated for the C2DP-covered graphite electrode, with capacity retention of 92.8% after 1000 cycles at 1 C and Coulombic efficiencies of > 99%. The feasibility of constructing artificial ion-regulating electrode skins with precisely customized two-dimensional polymers offers viable means to promote problematic battery chemistries.

Research into inorganic supramolecular chemistry is burgeoning, in particular that which focuses on the formation of capsular molecules and the effects that these unique environments have on catalytic reactions. With the aim of producing new ligand designs that could not only support reactive metals, but also partake in supramolecular aggregation to provide a capsular microenvironment, new tripodal ligands and wide span imines and amines have been synthesised. Furthermore, the exploitation of hydrogen-bonding motifs formed through pyrrole-imine tautomerisation upon metallation of these ligands has been explored, with the aim of enhancing reactivity and stabilising reactive intermediates. In Chapter one, the concept of covalent and non-covalent capsules is introduced, and includes the different aspects affecting the encapsulation of molecules and their use as nanoreactors. The use of secondary interactions, e.g. hydrogen-bonding in metal complexes of tetrapodal and tripodal ligands is discussed. Chapter two describes the synthesis of a tripodal pyrrole-imine ligand and the formation of its multi-metallic complexes of Group one metals, transition metal and the f-block elements. The complete and partial tautomerisation of this ligand upon metal complexation is also examined. In Chapter three, the formation of hangman complexes of the tripodal pyrrole-imine ligand is described and is extrapolated to the chemistry of a new pyrrole-amide ligand. The synthesis of this latter ligand and its properties with regards to anion binding are also explored. Chapter four describes the formation of wide span diamine and diimine ligands and their propensity to form adducts with cobalt and zinc chlorometallates and unusual multimetallic palladium complexes. The final conclusions of the work presented in this thesis are drawn in Chapter five. Chapter six presents experimental details and characterising data for all of the new compounds presented in this thesis.

This Thesis explores the topic of large amplitude motion within molecular machines and the different mechanisms and molecular architectures that are exploited in order to achieve control over the relative positions of submolecular components with respect to one another. Chapter One provides a thorough survey of a vast range of molecular switches and machines that have been developed during the last two decades. The focus is on interlocked and non-interlocked systems that display highly controlled large amplitude motion and the principles that govern their operation. Initially, simple molecular switches and shuttles are described with the chapter finally arriving at complex molecular machines such as motors, ratchets and walking molecules. The importance of understanding the different mechanisms that dictate the operation of switchable molecular machines and their fundamental differences are highlighted throughout the chapter. Chapters Two to Four are devoted to reporting the author’s contributions to novel switchable molecular systems. Chapter Two describes the serendipitous discovery of an ion-pair template which has been exploited in rotaxane formation and the operation of an orthogonal interaction anion-switchable molecular shuttle. The macrocycle moves back and forth along the thread between a cationic pyridinium station and a metal coordinating triazole motif when chloride anions are bound and removed respectively from a palladium centre which is located inside the cavity of the macrocycle. Excellent positional integrity (>98%) of the ring at both stations is achieved due to the orthogonal binding modes in the two states of the shuttle. Chapter Three presents a non-interlocked molecular switch that operates through the manipulation of dynamic covalent chemistry. The switch is comprised of a “two legged”, small organic molecule (a “walking unit”), anchored to a three foothold track via one disulfide and one hydrazone bond. The acid promoted hydrazone exchange allows a specific ratio of the two positional isomers to be achieved at equilibrium. However, the system is also arranged in such a manner that the ratio can be biased towards one positional isomer when the hydrazone exchange is carried out alongside the photoisomerisation (Z  E) of a stilbene motif which is incorporated in the track. The isomerisation alters the relative free energies of the products by increasing the ring strain of one positional isomer with respect to the other, hence introducing bias into the system. The final chapter reports the logical progression of the work presented in Chapter Three and describes the pursuit of a four-station dynamic covalent energy ratchet, of which the net position of the walker unit can be driven away from a steady state, minimum energy distribution by orthogonal disulfide and hydrazone exchange and concomitant stilbene isomerisation. The endeavour towards the successful synthesis of this rather complex molecule is described alongside the principles for its proposed operation. Chapter Two is presented in the form of an article that has already been published in a peer-reviewed journal. No attempt has been made to rewrite this work other than a slight alteration in the order of figures in the text to allow for easier reading and re-formatting to ensure consistency of presentation throughout this thesis. The original paper is reproduced, in its published format in the Appendix. Chapters Two, Three and Four begin with a synopsis to provide a general overview of the work that is presented in addition to a grateful acknowledgement of the contribution of my fellow researchers.

Eleven tested anions were able to form adducts with neutral oligosaccharides at low cone voltage in negative ion mode electrospray mass spectrometry. Among them, fluoride and acetate have the abilities to significantly enhance the absolute abundance of [M-H]- for neutral oliogosaccharides. The chloride adduct has the best stability among all the adduct species investigated. For the above three anions, CID of adduct species may be used for structural determination of neutral oligosaccharides. In the presence of F- and Ac-, simultaneous detection of acidic oligosaccharides and neutral oligosaccharides was achieved. The ratio of Cl- : non-Cl-containing product ions obtained in CID spectra of chloride adducts of disaccharides was used to differentiate anomeric configurations of disaccharides. Density functional theory (DFT) was employed to evaluate the optimized structures of chloride adducts of disaccharides. The formation and decomposition of chloride adducts with oligosaccharides of different acidities were investigated in MALDI mass spectrometry.

Direct methanol fuel cells (DMFCs) are considered a clean source of electrical power for future energy demand, creating a potential to reduce our dependency on fossil fuels. Despite their advantages, including high energy density, efficiency and easy handling and distribution of fuel, the commercialization of DMFCs has suffered from some drawbacks, including methanol crossover and contamination of the system. Metal cation contaminants (such as Ni, Co, etc) introduced through the degradation of fuel cell components (bipolar plate and electro-catalyst layer) can significantly affect the Nafion-membrane properties and overall fuel cell performance. In the current study, a systematic approach is taken to characterize and identify the mechanism of the effect of metal solution contaminants on the activities of electro-catalysts of DMFCs. Cyclic voltammetry and rotating disk electrode (RDE) techniques were utilized in order to characterize the effect of various concentrations (i.e., 2x10-x M (x=1-7)) of six metal solution contaminants (i.e., Co, Ni and Zn with sulfate and nitrate as counter-anions) on the voltammetric properties and electro-catalytic activity of polycrystalline Pt during methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). The results showed a decrease in the MOR and ORR activities of Pt as the concentration of metal solution increased. The effect of counter-anion on the Pt activity was further investigated. The results showed that a combined effect of counter-anions and metal cations may be responsible for the decrease in the electro-catalytic activity of Pt. The effect of metal solution contaminants on the Nafion-ionomer of anode electro-catalysts was investigated using Nafion-coated Pt electrode. Voltammetric properties and MOR activities of Nafion-coated and bare Pt electrodes in the presence of Ni solution contaminants were characterized using cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The overall results showed a significant negative effect of Ni solution contaminants on the electro-catalytic activity of bare Pt electrode as compared to the Nafion-coated Pt electrode. Based on the results, it appears that Nafion-ionomer film may interact with metal cations (through its sulfonate groups) and repel them away from the Pt active sites, partially inhibiting the negative effect of metal cations on the Pt activity of Nafion-coated Pt electrode. The effect of metal solution contaminants on the carbon-supported platinum nanoparticle (Pt/C) with various Nafion-ionomer distributions and contents (i.e., Nafion-incorporated Pt/C and Nafion-coated Pt/C electrodes) was further investigated. Cyclic voltammetry and EIS techniques were employed to characterize the effect of Ni solution contaminants on the voltammetric properties and MOR activities of Nafion-incorporated and Nafion-coated Pt/C electrodes. The overall results showed a stronger negative effect of Ni solution contaminants on the electro-catalytic activity of Nafion-incorporated Pt/C electrodes as compared to the Nafion-coated Pt/C electrodes. This further confirms previous observations showing the sulfonate groups of Nafion-ionomer film may attract the Ni metal cations, localize them away from the Pt active sites, and subsequently suppress the negative effect of cations on the activity of Nafion-coated Pt/C electrodes.

Immobilisation of functional entities, such as, enzymes, onto solid supports, as a means of facilitating their removal from the surrounding environment and subsequent regeneration has been in practice for many decades. This work focuses on the immobilisation and analysis of three-walled (pendant armed), cyclen based receptor complexes immobilised onto a silica surface for the purpose of sequestering aromatic anions from aqueous solution: Si-GPS-[Cd(Trac)](ClO4)2, Si-GPS-[Cd(DiPTrac)](ClO4)2, and Si-GPS-[Cd(TriPTrac)](ClO4)2 were the immobilised receptors used. Initially, synthesis of a three-walled model receptor, [Cd(TracHP12)](ClO4)2, that is not bound to silica yet mimics the properties of the silica anchored receptor complexes with a hydroxypropyl pendant arm was effected. Aromatic anion binding constant measurements were made on the model receptor using 1H NMR monitored titrations in DMSO-d6 which showed that, in comparison to the first generation four-walled receptors, the removal of one of the pendant arms did not affect the binding capability of the receptor's cavity significantly. It was shown that the binding strength correlated well with the pKa of the particular anion with, for example, p-hydroxybenzoate > m-hydroxybenzoate > o-hydroxybenzoate. The precursor to this receptor was then immobilised onto a silica surface and subjected to metal ion uptake studies to gauge its coordination properties with a number of divalent metal(II) ions: Cd(II), Pb(II), Zn(II), Cu(II) and Ca(II). The three Cd(II) coordinated receptor complexes mentioned above were then subjected to inclusion studies with a number of aromatic anions in aqueous conditions whereupon a reversal of the previously mentioned trend, i.e. o-hydroxybenzoate > m-hydroxybenzoate > p-hydroxybenzoate was observed. This indicated that the presence of water in the system changes the hydrogen bonding mode of the host-guest complexes, and was a major discovery arising from this work.

The activity of glutamate transporters is essential for the temporal and spatial regulation of the neurotransmitter concentration in the synaptic cleft which is critical for proper neuronal signaling. Because of their role in controlling extracellular glutamate concentrations, dysfunctional glutamate transporters have been implicated in several neurodegenerative diseases and psychiatric disorders. Therefore, investigating the mechanism of substrate transport by these transporters is essential in understanding their behavior when they malfunction. A bacterial glutamate transporter homologue has been successfully crystallized revealing the molecular architecture of glutamate transporters. However, many important questions remain unanswered. In this thesis, I will address the role of D439 in the binding of Na+, and I will identify other electrogenic steps that contribute to the total electrogenicity of the transporter cycle. The role of D439 in the binding of Na+ to the transporter was explored previously in this lab. While it was proposed that the effect of D439 in Na+ binding is indirect, the results described in this thesis provides added support to this work. Here, I will show that the D439 mutation changed the pharmacology of EAAC1 such that THA was converted from a transported substrate to a competitive inhibitor. I will also show that Na+ binding to the substrate-bound mutant transporter occurred with the same affinity as that of Na+ to the substrate-bound wild-type transporter. Therefore, based on these results, D439 is not directly involved in the binding of Na+ to the substrate-bound transporter, but that its effect is rather indirect through changing the substrate binding properties. Na+ binding steps to the empty transporter and to the glutamate-bound EAAC1 contribute only 20% of the total electrogenicity of the glutamate transporter reactions cycle. While K+-induced relocation has been proposed to be electrogenic, there is no experimental evidence that supports it. In this work, I will show that the K+-induced relocation of the empty transporter is electrogenic. Moreover, the results in this work show that the K+-dependent steps are slower than the steps associated with the Na+/glutamate translocation suggesting that the K+-induced relocation determines the transporter?s properties at steady state.

Research into anion-pi interactions has shifted from attempts to establish the legitimacy of the interaction to the incorporation of anion-pi interactions into supramolecular architectures. The research discussed in this dissertation explores the subtle effects of ligand, anion, and metal ion on supramolecular architectures of tetrazine-based ligands in the context of anion-pi interactions and their importance in the design and synthesis of supramolecular architectures. Computational studies highlight the importance of the arene quadrupole moment, molecular polarizability, and substituent effects on the strength of anion-pi interactions. More importantly, however, this work establishes that there is a distinct directionality inherent to the anion-pi interaction between polyatomic anions and N-heterocycles, which can be used to direct ligands in supramolecular architectures as demonstrated through the work of the Dunbar group in recent years, particularly that of the square and pentagonal metallacycles. The extension of metallacycles of bptz to CoII and FeII demonstrates the ability to tune the size of the metallacyclic cavity by simply changing the metal ion and results in the surprising encapsulation of two [SbF6]- anions in [Fe5(bptz)5(NCCH3)10][SbF6]10. 1H NMR spectroscopy and electrochemical studies reveal slight but significant differences characteristic of the square and pentagonal metallacycles and support the presence of anion-pi interactions in solution and highlight the importance of the encapsulated anion in the templation and stability of the metallacycles. A study of the interconversion between the square and pentagonal metallacycles via 1H NMR is presented for the first time. Increasing the pi-acidity of the chelating ligand from bptz to bmtz results in the encapsulation of only one [SbF6]- anion in [Fe5(bmtz)5(NCCH3)10][SbF6]10, maximizing anion-pi interactions with the ligand despite the tighter fit. A significant hurdle in the incorporation of different anions into the metallacyclic structures was overcome with the development of a new synthetic protocol for [Fe(NCCH3)6]2+ salts of a wide range of anions from sodium salts and Fe4Cl8(THF)6. Also, the nuclearity of the less stable [Fe5(bptz)5(NCCH3)10][PF6]10 metallacycle was established via a combination of MS, electrochemistry and 1H NMR experiments through comparisons with known FeII metallacycle solution behavior.

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