Inorganic Chemistry Commons^™

Luminescent Group 11 Metal (I) Chalcogen Clusters With A Conjugated Diphosphine Ligand, Kai Yu Jeffrey Li

Electronic Thesis and Dissertation Repository

Polynuclear Au (I) complexes exhibit rich photochemical properties and have the potential to find applications as molecular sensors, switches, or energy storage devices. Although dinuclear Au (I) complexes with bridging diphosphines have been extensively examined, most of those reported do not contain rigid-diphosphine ligands.

This thesis examines how the rigid diphosphine, 4,6-bis(diphenylphosphino)dibenzofuran (DBFDP) can be incorporated for the controlled assembly of photoluminescent gold (I) metal – chalcogenolate (chalcogenolate = RS^-, RSe^-; R = organic moiety) and gold (I) chalcogenide (chalcogenide = S^2-, Se^2-) bimetallic complexes. In these studies, the chalcogen …

Exploring The Reactivity Of Metal-Ligand Cooperative Complexes With Dioxazolones, Terminal Alkynes, And 2-Ethynylbenzyl Alcohol, Megan A. Hoffer Miss

Electronic Thesis and Dissertation Repository

N-Acyl ketenimines were attempted to be synthesized catalytically by [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ with phenylacetylene and 3-phenethynyl-1,2,4-dioxazol-5-one. Trapping agents were employed to identify the major product of the reaction, as many products were formed. [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ reacts with 3-phenethynyl-1,2,4-dioxazol-5-one generating an isocyanate via the Curtius rearrangement, confirmed by a forced Curtius rearrangement with 3-phenethynyl-1,2,4-dioxazol-5-one and 1,2,4-triazole. Rates of vinylidene formation using [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ and various terminal alkynes of different sterics and electronics were evaluated using a Hammett analysis for and simple rate comparisons. …

Investigating The Structure Of Metal-Organic Frameworks And The Behaviors Of Adsorbed Guest Molecules In Mofs Via Solid-State Nmr Spectroscopy, Yihao Shen

Electronic Thesis and Dissertation Repository

Metal-organic frameworks (MOFs) are a class of hybrid organic-inorganic microporous materials with lots of significant applications including gas capture and storage, gas separation, batteries, catalysis, ion exchange and drug delivery. MOFs based on s-block metals are important due to their many practical applications. These MOFs are also very interesting because the s-block MOFs often exhibit unpredictable behavior of coordination. In this thesis, the structures of six s-block metal (Li, Na, Cs, Mg, Ca, Sr) based MOFs involving V-shaped link, 4, 4′- sulfonyldibenzoate (SDB) are characterized by various techniques including, powder X-ray diffraction, TGA and solid-state NMR spectroscopy. ¹³C CPMAS …

Synthesis Of Ni(Ii) Complexes For Allylic C(Sp3)-H Bond Activation For Aerobic Oxidation Catalysis, Shagana Kukendran

Electronic Thesis and Dissertation Repository

Nickel is a widely abundant and inexpensive metal. Catalysts are substances that remain unconsumed and increase the rate of reactions by reducing the activation energy barrier, often by providing an alternative route. The main goal of this study is to prepare Ni(II) complexes that can promote a catalytic aerobic oxidation reaction by breaking allylic C-H bonds. Based on previous studies, allylnickel N-heterocyclic carbene complexes react with molecular oxygen to give useful carbonyl compounds with a Ni(II)-OH by-product, which undergoes dimerization. In order to achieve catalysis, dimerization of the Ni(II)-OH should be prevented and C-H activation has to be achieved to …

Synthesis And Surface Modification Of Azide Decorated Silver Nanoclusters, Alexander H. Stöckli

Electronic Thesis and Dissertation Repository

In nanocluster research, easy modification of the cluster surface while maintaining the cluster core remains a key challenge. Herein we report the synthesis, structure, and properties of four targeted Ag₂₀ nanoclusters (NCs) with surface azide moieties, two of which have 8 azide moieties, [CO₃@Ag₂₀(S^tBu)₁₀(m-N₃-C₆H₄COO)₈(DMF)₄] and [CO₃@Ag₂₀(S^tBu)₁₀(p-N₃-C₆H₄COO)₈(DMF)₄], and two of which have 6 azide moieties, [CO₃@Ag₂₀(S …

The Synthesis, Lewis Acidity And Catalytic Activity Of Bis(Catecholato)Germanes, Andrew T. Henry

Electronic Thesis and Dissertation Repository

Main group Lewis acids have been shown to be viable alternatives to state-of-theart transition metal catalysts. While extensive research into a variety of p-block Lewis acids have been reported, the field of germanium Lewis acid chemistry has been described as “almost non-existent”. A variety of bis(catecholato)germane derivatives have been synthesized. The Lewis acidity of these compounds was analyzed by the Gutmann-Beckett and fluoride ion affinity methods demonstrating the high Lewis acidity of these complexes. The bis(catecholato)germanes were utilized as Lewis acid catalysts for the hydrosilylation of aldehydes, the hydroboration of alkynes, Friedel-Crafts alkylation of alkenes, and the oligomerization of styrene …

The Coordination Chemistry And Reactivity Of Pd Phosphine 1-Azaallyl Complexes, Kyle M. Jackman

Electronic Thesis and Dissertation Repository

Structurally responsive ligands (SRLs) are a class of ligands that change their coordination mode with a metal centre, which permits reactions that are difficult with non-SRLs, allow access to unique mechanisms, and allow isolation of unusual coordination complexes. The 1-azaallyl (1-AzA) family of SRLs are capable of isomerizing between η³-NCC and κ¹-N modes that occupy two and one coordination sites, respectively. This thesis investigates a new class of phosphine 1^AzA (P^AzA) ligands and the reactivity of their coordination complexes with palladium.

The first-generation P^AzA ligand contains a phenyl linkage between the two heteroatoms and affords a …

Bismuth Binding In Human Metallothionein, Emily M. Toswell

Undergraduate Student Research Internships Conference

Bismuth metal is one of the least toxic heavy metals for humans. It is used in a wide variety of applications including organic synthesis, cosmetics and pharmaceutical applications. In biomedicine, bismuth is a therapeutic metal used in metallodrugs such as Pepto Bismol for its antimicrobial and antibacterial properties. Metallothionein (MT) is a cysteine rich protein found in the liver, kidneys, brain and central nervous system. MT can bind a variety of metals including essential metals such as zinc and copper. This research investigates the binding pathway of Bi[EDTA]- with fully metallated Zn₇MT by using mass-spectrometry and UV-vis absorption.

Design And Surface Modification Of Noble Metal-Based Nanocatalysts, Xuchun Wang

Electronic Thesis and Dissertation Repository

This thesis investigates approaches to modifying the surface structure of noble metal-based nanocatalysts. Noble metal-based nanocatalysts, such as Pt and Pd, play a significant role in heterogeneous catalysis due to their capabilities in activating the cleavage or formation of chemical bonds, but still suffer from the high-cost issue and unsatisfied catalytic performance due to too strong or too weak adsorption of intermediates. Considering the surface specificity of heterogeneous catalysis, Bi, a cheap metal, was used to modify the surface of Pt- and Pd-based nanocatalysts. This thesis aims to unveil the role of Bi in improving their catalytic performance from both …

Investigating The Influence Of Synthetic Environments On The Electronic Structure And Luminescence Of Cr-Doped Zinc Gallate, Xincheng Li

Electronic Thesis and Dissertation Repository

Cr doped ZnGa₂O₄ (Cr-ZGO) has shown potential in the field of bioimaging. To achieve the nano-size suiting for bioimaging, Cr-ZGO is normally synthesized using a hydrothermal method. There are few studies on how the hydrothermal conditions influence the structure and optical properties of the Cr-ZGO. The first two parts of this thesis study how different hydrothermal temperatures and pH environments will affect the optical properties of Cr-ZGO by photoluminescence spectroscopy. By combining the electronic structure information extracted from X-ray absorption near-edge structures (XANES) and extended X-ray absorption fine structure (EXAFS), a relationship among hydrothermal conditions, optical properties …

Solid State Nmr Spectroscopic Characterization Of Metal Organic Frameworks, Vinicius Martins

Electronic Thesis and Dissertation Repository

Metal-organic frameworks are porous organic-inorganic materials that have attracted enormous attention due to their promising capabilities for several technologies, including carbon dioxide capture and storage, gas separation, and heterogeneous catalysis. The performance of MOFs for these applications is directly linked to their properties and, by extension, structures. Therefore, it is essential to understand the structure – property relationship. Solid-state NMR (SSNMR) spectroscopy is a technique that provides complementary information to X-ray diffraction-based techniques. SSNMR can provide short-range information around the NMR-active nucleus of interest. Furthermore, SSNMR can provide additional information regarding host-guest interactions and dynamics of adsorbed molecules, which play …

The Effects Of Solution Ph, Temperature And Redox Environment On Corrosion And Oxide Formation On Inconel X-750, Mohsen Bahrami

Electronic Thesis and Dissertation Repository

Nickel-based superalloys have a wide range of applications in different industries due to their exceptional mechanical and corrosion-resistance properties. These alloys are widely employed in the nuclear industry. Inside a nuclear reactor, these alloys are exposed to a continuous flux of gamma-radiation. When exposed to gamma-radiation, water decomposes, resulting in the production of oxidizing and reducing species. These species have a considerable effect on the redox chemistry of the solution, which controls the overall corrosion behaviour of nickel-based superalloys.

Corrosion of metals and alloys involves several elementary steps. A comprehensive understanding of these steps and how they influence each other …

Metal Ligand Cooperative Complexes For Acceptorless Dehydrogenation Of Amines, Matthew D. Hoffman

Electronic Thesis and Dissertation Repository

Complexes of the type [M(Cp/Cp*)(MeCN)(P^R₂N^R′₂)]PF₆ (M = Fe, Ru) were synthesized and/or tested towards acceptorless dehydrogenation (AD) of amines. The primary amine benzylamine can undergo AD to form a mixture of products, and a selection of catalysts were employed in an attempt to control product selectivity. As a result, trends in product distribution were observed by modifying the primary and secondary coordination spheres on the catalyst. A new complex, [Fe(Cp)(MeCN)(P^Ph₂N^Ph₂)]PF₆ (3a) was synthesized and characterized and was found to be a completely selective dehydrogenation …

Effects Of Gamma-Radiation On The Evolution Of Copper Corrosion Dynamics In Deep Geological Repository Solution Environments, Lindsay J. Grandy

Electronic Thesis and Dissertation Repository

The Canadian plan for permanent disposal of used nuclear fuel involves a used fuel container (UFC), a carbon steel vessel with a copper coating to provide the corrosion protection. The corrosion conditions for the copper layer of the UFC are expected to involve small, stagnant water volumes, pH values between 6 and 9, and a continuous flux of γ-radiation emitted from the radionuclides trapped in the fuel matrix. While γ-radiation does not affect the copper metal directly, humid air and water will radiolytically decompose into redox-active and acidic species which will be produced at constant concentrations and can alter the …

Functional Nanoparticles: Tin Monoxide And Molybdenum Disulfide Quantum Dots On Graphene Nanosheets, Denys Vidish

Electronic Thesis and Dissertation Repository

Light harvesting can be referred to the use of an ensemble of different nanoparticles, or quantum dots, or other absorbers to optimize the ability to capture a given spectrum of electromagnetic radiation (for example the solar spectrum under specific atmospheric conditions) in a light-absorbing system. To this end, different nanoparticles play complementary functions within the system and absorb or scatter light at different wavelength intervals. Light harvesting finds applications in fields as diverse as solar cells, photosynthesis and photocatalysis. Graphene supporting a set of different semiconducting nanoparticles has often been proposed as light harvesters. To further this concept, my thesis …

Lithium Dubbed Cspbbr3 Perovskite Nanocrystals, Siena Idoine

Undergraduate Student Research Internships Conference

No abstract provided.

Synthesis Of Photoluminescent Metal-Chalcogen Clusters For Potential Oled Applications, Aaron Mitchell

Undergraduate Student Research Internships Conference

No abstract provided.

Cyclization Of Peptide Structures By Creating Metal Foldamers Using 99m-Tc/Re(Co)3, Dhvani D. Oza

Electronic Thesis and Dissertation Repository

Constrained peptides have been successful as therapeutics owing to the rigidity in their framework, allowing them to have enhanced pharmacological properties. Apart from covalent bond based cyclization, constraints can be induced by cyclization using metal coordination. The metals Re and ^99mTc are one of the few metals which have not been studied in great detail for their ability to cyclize linear peptides. A tri-alanine sequence was employed in the peptide backbone due to its ability to form stable helices. In addition, another tripeptide sequence RGD, which is recognized by the integrin a_vb₃, was also used. …

Electronic And Local Structures Of Pt-Based Bimetallic Alloy And Core-Shell Systems, Jiatang Chen

Electronic Thesis and Dissertation Repository

This thesis investigates the electronic structure of Pt for catalysis applications. The importance of the Pt 5d band is discussed in terms of the bonding capability of Pt. The oxygen reduction reaction in proton exchange membrane fuel cells is chosen as the catalytic reaction model to illustrate the effect of Pt 5d states on Pt-O interaction. Pt-based bimetallic systems are introduced as a solution for the high price and limited resources of Pt. Despite lower usage of Pt, the tuning capability to optimize the Pt 5d band in bimetallic catalysts is supposed to provide superior catalytic activity. Advanced synchrotron X-ray …

Iron(Ii) Metal-Ligand Cooperative Catalysts For Endo-Selective Intramolecular Hydrofunctionalization, Benjamin Bridge

Electronic Thesis and Dissertation Repository

Two new cationic Fe(II) P^R₂N^R'₂ complexes, [Fe(Cp*)(P^R₂N^Ph₂)(MeCN)]PF₆ (R = cyclohexyl, 3a) and [Fe(Cp*)(P^R₂N^Ph₂)(MeCN)]PF₆ (R = phenyl, 3b), were synthesized and characterized. The catalytic activity for intramolecular hydrofunctionalization was tested using the benchmark substrate 2-ethynylaniline (EA) and both catalysts effectively produced indole (Ind). The selectivity of catalysis was also tested using 2-ethynylbenzyl alcohol (EBA) and both catalysts formed only the endo product isochromene (IC). These complexes represent the first well-defined Fe(II) catalysts that …

N-Heterocyclic Carbene Ligated Group 11 Trimethylsilylchalcogenolates: Building Blocks For Heterometallic Chalcogenide Molecules, Dickron Richard Nahhas

Electronic Thesis and Dissertation Repository

The synthesis of heterometallic chalcogenide molecules requires the continued investigation into the appropriate reagents necessary to introduce metal – chalcogen bonds in a controlled fashion. Trimethylsilyl metallochalcogenolates (MESiMe₃) act as synthons introducing “ME^–“ in solution upon reacting with an appropriate ternary metal reagent, MX (X= halide, acetate, etc.). Recent work makes use of N–heterocyclic carbenes (NHCs) as a class of ancillary ligand that can stabilize these reagents and the heterometallic chalcogenide molecules obtained with them. Building on previous work, this thesis describes the synthesis of group 11 trimethylsilyl metallochalcogenolates stabilized by bis–1,3–tritylimidazole–2–ylidene (abbreviated ITr) …

High-Pressure Studies On The Transition From Red Phosphorus To Black Phosphorus, Heng Xiang

Electronic Thesis and Dissertation Repository

Black phosphorus (BP) is a promising material in many research fields. However, the transition process from amorphous red phosphorus (ARP) is elusive and hence hinders large scale synthesis and applications. This work describes the application of the high-pressure method to study the transition process from ARP to BP.

In this thesis, the following three objectives were achieved: (1) to understand the mechanism of the transition, (2) to facilitate the synthesis of BP by taking the advantage of less pure ARP, (3) to propose new methods of synthesizing BP-based materials, such as the moderately oxidized BP and the black phosphorus/ amorphous …

Investigations Of The High Pressure Effects On Structural Properties And Co2 Adsorption Performance Of Mofs Using Vibrational Spectroscopy, Shan Jiang

Electronic Thesis and Dissertation Repository

The pre- and post-combustion carbon dioxide capture has drawn much attention in the past few decades owing to the increasing concentration of CO₂ in the atmosphere. Among all the potential solid adsorbents for CO₂ capture, metal-organic frameworks (MOFs) are a promising class of materials due to their large surface areas, high tunability and their high selectivity for gas adsorption applications. It has been widely demonstrated that the application of high external pressure in gigapascal level can substantially tune the structure, pore size and opening of porous material. Consequently, the structural, as well as gas adsorption properties of these …

Progress Toward Durable Icephobic Materials, Matthew J. Coady

Electronic Thesis and Dissertation Repository

Ice accumulation is a major engineering challenge in many fields including aerospace, power generation, transportation, and infrastructure. A variety of solutions are being researched to address this challenge. Perhaps the most promising method of combating ice accumulation is by applying coatings with low values of interfacial ice adhesion strength, τ_ice. Icephobic materials are those with ice adhesion below 100 kPa, and it has been shown that passive delamination can occur on surfaces with τ_ice below 20 kPa. While various low adhesion surfaces have been prepared, durability concerns pervade applications where surfaces experience repeated icing or freeze-thaw cycles, …

Zinc–Phosphorus Clusters For Solution Synthesis Of Zinc Phosphide Nanoparticles, Kyungseop Lee

Electronic Thesis and Dissertation Repository

Synthesis of zinc phosphide (Zn₃P₂) nanoparticles is an emerging topic of investigation as Zn₃P₂ is a candidate material for the next generation solar cells. Despite the early discovery of its favorable electronic properties that are well-suited for photovoltaic applications, a major focus of synthetic strategy was with vapor/chemical deposition methods. Solution methods with greater control over size, crystal structure and composition at a lower production cost, has been underdeveloped in comparison. In this context, this thesis describes the synthesis, characterization and reactivity of zinc phosphido clusters: [Zn₂(μ-PPh₂)₂(PPh …

Methodologies For Metal Functionalization Of Phosphorus Based Photopolymer Networks, Vanessa Béland

Electronic Thesis and Dissertation Repository

Photopolymer networks with phosphonium cation, alkyl phosphine and olefin functionality were designed, synthesized and functionalized with metals by metathesis, coordination and hydrometallation reactions, respectively. The materials were strategically designed so that the metal functionalization step could be monitored and quantified. In some cases, this involved characterization by IR, NMR, or X-ray spectroscopic techniques, or by comparison to molecular analogues. It was found that by using a bi-functional photopolymer network, the material could be bi-metallized by orthogonal mechanisms. All metallized polymer networks were tested for their suitability as precursors to metal-containing ceramics. The polymers were pyrolyzed, and on analysis it was …

The Reactivity Of Ditetrelenes Towards Organophosphorus Oxides, Maissa Belcina

Electronic Thesis and Dissertation Repository

The reactivity of tetramesityldisilene 4 and tetramesityldigermene 5 towards organophosphorus oxides was explored in this thesis. The reaction of dialkyl and diarylphosphine oxides and phosphites with ditetrelenes 4 and 5 resulted in a 1,3-addition to form diorganodisilyl and digermyl phosphinites 27, 28, 31, 32 and disilyl phosphites 35 and 36. The 1,3-addition resulted in a mild two electron reduction of the P(V) centre of the phosphine oxide and phosphite to a P(III) centre in the products, without the use of heat or a catalyst. The reaction of organophosphorus oxides provides another example of a main group …

Synthesis, Characterization, And Applications Of Group 13 And 14 Complexes Of Chelating Formazanate Ligands, Ryan R. Maar

Electronic Thesis and Dissertation Repository

This thesis describes the synthesis and characterization of group 13 (boron and aluminum) and group 14 (silicon, germanium, and tin) complexes supported by chelating formazanate [R¹-N-N=C(R³)-N=N-R⁵]^‒ ligands. The resulting complexes are redox-active and often luminescent. Chapters two to four describe the synthesis and characterization of boron formazanate adducts. The work in these chapters demonstrates that through structural modification of the formazanate ligand, solid-state- and NIR photoluminescence can be achieved. Furthermore, the formation of an oxoborane (B=O) afforded a highly photoluminescent formazanate adduct due to the structural rigidity imposed by the B=O bond. These …

Non-Traditional Metallation Of Metallothioneins With Xenobiotic Therapeutic Metals, Daisy L. Wong

Electronic Thesis and Dissertation Repository

The rise of the Anthropocene has seen more global pollution than before in history. With the explosion of consumer electronics in the last half century, the rise of metal pollution from their extraction and disposal results in the unnatural introduction of heavy and rare metals into the ecosystem. Organisms have a metal defense protein, metallothionein, which has multiple roles in essential metal regulation and protection against minimal toxic metal exposure. However, these modern heavy metals prominent in electronics are not found biologically and their interactions in the body are generally unknown. Some of these metals are employed as therapeutic agents …

Development Of In Situ Forming Hydrogels For Intra-Articular Drug Delivery, Andy Prince

Electronic Thesis and Dissertation Repository

Hydrogels are 3-dimensional crosslinked polymer networks that can absorb significant amounts of water. The physical properties associated with hydrogels affords them resemblance to biological tissues making them good candidates for biomedical applications. Many pharmaceuticals, specifically non-steroidal anti-inflammatory drugs (NSAIDs), have poor aqueous solubility, which limits their bioavailability and efficacy. People suffering from chronic osteoarthritis (OA) are required to frequently take large doses to mitigate pain, which can lead to serious side effects. Hydrogels are good strategies to deliver NSAIDs via articular injection because they can form solid gels in situ. This thesis describes the synthesis, formulation, mechanical testing, in …