abstract: Structural details of phosphonic acid functionalized nanomaterials and protic ionic liquids (PILs) were characterized using nuclear magnetic resonance (NMR) spectroscopy. It is well known that ligands play a critical role in the synthesis and properties of nanomaterials. Therefore, elucidating the details of ligand-surface and ligand-ligand interactions is crucial to understanding nanomaterial systems more completely. In an effort to further the understanding of ligand-surface interactions, a combination of multi-nuclear (1H, 29Si, 31P) and multi-dimensional solid-state NMR techniques were utilized to characterize the phosphonic acid functionalization of fumed silica nanoparticles using methyl phosphonic acid (MPA) and phenyl phosphonic acid (PPA). Quantitative 31P MAS solid-state NMR measurements indicate that ligands favor a monodentate binding mode. Furthermore, 1H-1H single quantum-double quantum (SQ-DQ) back-to-back (BABA) 2D NMR spectra of silica functionalized with MPA and PPA indicate that the MPA and PPA are within 4.2±0.2 Å on the surface of the nanomaterial. The ligand capping of phosphonic acid (PA) functionalized CdSe/ZnS core-shell quantum dots (QDs) was investigated with a combination of ligand exchange, solution and solid-state 31P NMR spectroscopy. In order to quantify the ligand populations on the surface of the QDs, ligand exchange facilitated by PPA resulted in the displacement of the PAs, and allowed for quantification of the free ligands using 31P liquid state NMR. In addition to characterizing nanomaterials, the ionicity and transport properties of a series of diethylmethylamine (DEMA) based protic ionic liquids (PILs) were characterized, principally utilizing NMR. Gas phase proton affinity was shown to be a better predictor for the extent of proton transfer, and in turn the ionicity of the PIL, than using ∆pKa. Furthermore, pulsed field gradient (PFG) NMR was used to determine that the exchangeable proton diffuses with the cation or the anion based on the strength of the acid used to generate the PILs. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2015

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Ionic liquids (ILs) were studied as solvents for electrochemical reactions with the intent to devise metallurgical processes for Al, Mg and Ti that are less energy intensive and operate at lower temperatures than current industrial practice. Tetra-alkyl phosphonium ILs are on the low end of the IL cost spectrum and are regarded as understudied compared with imidazolium and pyridinium ILs. They are also known to be more thermally stable. The density, viscosity and conductivity of the phosphonium ILs and metal salt-IL mixtures were measured. The conductivity of the phosphonium ILs tested were found to be roughly an order of magnitude lower than imidazolium ILs; this is attributed to the relatively large cation size and localized charge. Linear density-temperature functions are presented. The viscosity and conductivity temperature relationship was modeled using the Vogel-Tamman-Fulcher (VTF) equation. The electrochemical window of A10341'14,6,6,610 was studied on a Pt substrate over a wide range of A1C13 concentrations using cyclic voltammetry (CV). It was found that the tetra-alkyl phosphonium cation is on the order of 800 mV more electrochemically stable than the 1-ethyl-3-methyl imidazolium (EMI+). Cathodic and anodic polarization of Al in A1C13-[P14,6,6,6]C1 (Xmc13 = 0.67) was studied at temperatures ranging from 347 to 423 K. The Butler-Volmer equation was fitted to the plots by varying the kinetic parameters. The cathodic reaction was found to be diffusion limited and the anodic reaction is limited by passivation at lower temperatures. The overpotential required for electrodissolution of Al was found to be higher than for electrodeposition. Aluminium was electrodeposited using both an electrowinning setup (chlorine evolution anode reaction) and electrorefining setup (Al dissolution anode reaction). The deposits were characterized in terms of morphology, current efficiency and power consumption. A variety of deposit morphologies were observed ranging from smooth, to spherical to dendritic, and in some cases, the IL was occluded in the deposit. The current efficiency and power consumption were negatively impacted by the presence of H2O and HCl present in the as-received ILs and by C12(g) generated by the anode reaction in the case of the electrowinning setup. HC1 was removed by cyclic polarization or corrosion of pure Al, resulting in current efficiencies above 90%. Aluminium was electrodeposited using the electrorefining setup with anode-cathode spacing of 2 mm at power consumption as low as 0.6 kWhr/kg-Al. This is very low compared with industrial Al electrorefining and Al electroplating using the National Bureau of Standards bath, which require 15-18 kWhr/kg-Al and 18 kWhr/kg-Al, respectively. However, due to low solution conductivity the power consumption increases significantly with increased anode-cathode spacing. Titanium tetrachloride was found to be soluble in [P14,6,6,6]Cl and increases the conductivity of the solution. Attempts to reduce the Ti(IV) included corrosion of titanium metal, corrosion of magnesium metal powder and cathodic polarization. Despite a few attempts, the electro-deposition of Ti was not observed. At this point, titanium electrodeposition from phosphonium based ILs does not appear feasible. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

The philosophy of green chemistry has seen much development in the past decade. The use of environmentally benign solvents is amongst the areas of green chemistry that have received the most attention. In this context, imidazolium ionic liquids have been widely reported to offer high product yields, fast reaction rates, excellent selectivity and generally mild working conditions, when used as reaction media. In addition, concerns about costs of solvents and the long-term environmental impact that can potentially result when solvents are discarded after their use have led to focused investigations into solvent-free procedures, as reported in recent literature. We have set out to explore the extent to which these advantages could be realized within our research. Non-volatile, non-flammable imidazolium ionic liquids [bmim][I], [bmim][BF4] and [bmim][PF6] were used as green solvents in ferrocene chemistry. Ferrocenoate esters were synthesised efficiently by the respective DCC/DMAP-promoted reactions of ferrocenecarboxylic acid and substituted benzoic acids or, alternatively, the DMAP-promoted reactions of ferrocenoyl fluoride with a range of substituted phenols in [bmim][BF4] and [bmim][PF6]. High yields and short reaction times were achieved. In addition, the ionic liquid was reused several times without a reduction in product yields. Under solvent-free conditions, DCC/DMAP-promoted reactions provided high yields within 3 min of reaction. The possible rearrangement of one of the intermediates in these reactions was modelled theoretically using density function theory (DFT) at the B3LYP/6-31G* level of approximation. Catalyst-free esterification was achieved by the application of microwave radiation to the reaction of ferrocenoyl fluoride and a range of substituted phenols. All the reactions were complete after 1 min of irradiation and products were isolated in high yield. DPAT, HfCl4, Sc(OTf)3 and Al(OTf)3 were screened as catalysts for esterification in [bmim][BF4] and under solvent-free conditions at various temperatures. All attempts at esterification of ferrocenecarboxylic acid with alcohols and phenols were unsuccessful. The Suzuki cross-coupling reaction was carried out in [bmim][BF4]. The isolated yields are, however, poor and suffer from poor reproducibility with different batches of [bmim][BF4] used.

The IL’s used in this study were either synthesized or commercially available. Preparation of the IL’s involved 2 step processes: firstly the heating of distilled 1-methylimidazole with distilled 1-chlorobutane under reflux to obtain 1-butyl-3- methylimidazolium chloride; secondly, the metathesis reaction of sodium tetrafluoroborate with 1-butyl-3-methylimidazolium chloride to obtain 1-butyl-3- methylimidazolium tetrafluoroborate. The addition of sodium tetrafluoroborate, sodium hexafluorophosphate and lithium trifluoromethane sulfonamide with 1-butyl-3-methylimidazolium chloride produced good yields of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide respectively. The IL’s are hygroscopic and must be stored under a nitrogen atmosphere. The IL’s were analyzed using 1H and 13C NMR analysis with CDCl3 as solvent. The physical and chemical properties of these IL’s were compared to commercial products. The physical and chemical properties compared well to reference values from the literature. The physical properties measured include the density, conductivity and electrochemical window. The electrochemical window is dependant primarily on the resistance of the cation to reduction and the resistance of the anion to oxidation. The electrochemical windows of the IL’s were very similar to the reference windows obtained from literature and it can be seen that some IL’s have a slightly lower window which can be due to water present. Water content in the IL’s was determined with the use of a Karl Fischer titrator, with Hydranal 5 Composite as titrant and HPLC grade methanol as the base. The concentration of halide in the IL’s was determined with a Perkin-Elmer ICP-MS.

This research explored the amination reaction of 1,3-bis-chloromethyl-tetramethyl-disiloxane in two different pathways. First, will discuss the synthesis of a new bipodal amino siloxane ligand which was achieved by the reaction of bis-chloromethyl-tetramethyl-disiloxane with t-BuNH3 in the presence of n-BuLi. The new ligand, of t-Butyl-[3-(t-butylamino-methyl)-1,1,3,3-tetramethyl disiloxanylmethyl]-amine (L1), is a model ligand designed to simulate the SOMC model of silica support and bipodal amido ligand that has been presented by the Basset group. Hence, developing this type of siloxane ligand and their complexes will be valuable in the synthesis of new homogenous catalyst, studying the reactivity and attempt to connect them with the SOMC examples. For this, the reaction of L1 with several Lewis acids and afforded several uncommon dimer and cluster complexes in the solid state. The second part of this research found that heating of bis-chloromethyl-tetramethyl-disiloxane with a 4-6 equivalent of amine, affording 4-N-Alkyl-tetramethyl- oxazadisilinane as six heterocycle ring by using a new simple and neat method. Using six different amine functional groups afforded six new oxazadisilinane compounds with different alkyls substituted. Each oxazadisilinane compound was utilized and reacted with four different acids, affording a series of twenty-one examples of new siloxane protic ionic liquids (Si-PILs). Also, the reaction of the cation with methyl iodide provided two examples of siloxane aprotic ionic liquids (Si-AILs). The new family of Si-ILs were well characterized by using NMR, mass, melting point, elemental analysis and thermal gravimetric analyses. Additionally, twelve crystals were suitable for X-ray diffraction as Si-PILs and one for Si-AILs. By studying their chemical and physical properties, a good library of the new Si-ILs has been built. Finally, one group of the new Si-PILs was used for butyl acetate esterification. The 5-X group of new Si-PILs salt was tested for esterification of butanol with acetic acid by thermal heat and under microwave irradiation. The salt 5-BF4- showed a good result in both systems with easy separation from the reaction mixture and recyclability discriminates the 5-BF4- as a good catalyst for the esterification reaction.

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This diploma thesis is focused on proposal and actual creation of mobile application to support in-house processes, especially for improving ordering and delivery processes inside of small company. Thesis includes analysis of current state of processes and analysis of client’s requirements. Based on those requirements, mobile application is created, built with Ionic and Angular framework.

Since the discovery of organic semiconductors (OSCs) over four decades ago, the field of organic electronics has broken our misconceptions regarding the possibilities of modern electronics. The synthetic toolkit of organic chemistry enables the creation of a limitless number of unique OSCs that can be specifically tailored and engineered with the specific and desired properties for unique applications. The rapid adoption of modern information systems, “Internet of Things,” in which smart devices and sensors ubiquitously collect and exchange data has resulted in a need for low-cost sensors to be deployed everywhere from the monitoring of food supply chains, environmental conditions, to human health. Organic thin-film transistors (OTFTs) are a necessary component to support these technologies. However, their mass adoption will require reduction in cost and improved compatibility with low voltage generating printed batteries or flexible and ultrathin photovoltaics. This thesis is focused on the development of high performing solid state polymer electrolytes to be employed as the gating medium in OTFTs. The choice of conventional gating materials often leads to a tradeoff between high capacitance, operating speed and material softness. For example liquid electrolyte gating materials have high capacitance but low operating speed and are liquid at room temperature which is unacceptable for many electronics application. Polymer gating materials often have lower capacitance but fast operating conditions and solid at room temperature. In this thesis we establish structure property relationships which aid in the design of novel block copolymer-based gating materials which simultaneously enable the increase in capacitance and switching speed while remaining solid at room temperature. In the first study I established a styrene-based ionic liquid monomer can be using as a controlling monomer in the nitroxide mediated copolymerization of methacrylates. The second study then focuses on the integration of these materials into OTFT devices; the morphology (block vs random copolymers) effect on device performance is assessed. The last study builds on the findings of the previous study and further explores the structural elements of block copolymers on device performance. The work presented here outlines the development of advanced poly(ionic liquid) based solid electrolyte materials that enables both reduced operating voltages and fast switching. Finally, we establish structure-property relationships that relate the molecular architecture to OTFT device performance paving the way for the adoption of a new generation of high performing, printable and flexible electronics.