Inorganic Chemistry Commons^™

Ultrafast Spectroscopy And Energy Transfer In An Organic/Inorganic Composite Of Zinc Oxide And Graphite Oxide, Jeff A. Secor

Dissertations, Theses, and Capstone Projects

The energy transfers and nature of defect levels of an organic/inorganic composite of Zinc Oxide and Graphite are studied with multidimensional spectroscopy. The edge and surface states of each composite are uncovered using excitation emission experiments showing which defect states are mediating the energy transfer from the metal oxide to the graphite oxide. Multidimensional time resolved spectroscopy further describes the effect of the carbon phase on the energy transfer pathways in the material.

Preparation, Characterization, Electrochemistry, And Infrared Spectroelectrochemistry Of Ruthenium Nitrosyl Porphyrins Containing Η1-O Bonded Axial Carboxylates, Dennis Awasabisah, Nan Xu, Krishna P. Sharmah-Gautam, Douglas R. Powell, Michael J. Shaw, George B. Richter-Addo

SIUE Faculty Research, Scholarship, and Creative Activity

The synthesis, characterization and redox behavior of eight low-spin nitrosyl carboxylate compounds (por)Ru(NO)(η¹-OC(=O)R) (por = T(p-OMe)PP: R = Me (1), i-Pr (2), t-Bu (3), p-C₆H₄NO₂ (4), Fc (5), CF₃ (8); por = TTP: R = Fc (6)) and (T(p-OMe)PP)Ru(NO)(OC₆HF₄) (7) are reported. The compounds are moderately stable in air as solids. Their IR (KBr) spectral data show ʋNO's in the 1839-1861 range cm^-1. The X-ray crystal structures of compounds 1 …

New Approaches To Chalcogenide Materials For Thermoelectrics: Lead Telluride-Based Nanostructures And Facile Synthesis Of Tetrahedrite And Doped Derivatives, Derak Justin James

Wayne State University Dissertations

The overall purpose of this work is to address several of the roadblocks to use of thermoelectric materials for generation of electricity, namely inefficient processing of materials and low performance, commonly rated by the figure of merit, ZT=T2/tot. The ZT includes  as the Seebeck coefficient,  as electrical resistivity, T as the average temperature, and tot as total thermal conductivity. tot is the sum of electronic charge carrier (C) and lattice (L) contributions to thermal conductivity. Attempts to increase ZT in the literature to values >1 have focused on decreasing the thermal conductivity via nanostructuring or optimizing the electrical …

Design Of First-Row Transition Metal Bis(Alkoxide) Complexes And Their Reactivity Toward Nitrene And Carbene Transfer, James Bellow

Wayne State University Dissertations

The novel alkoxide ligand [OCtBu2Ph], or [OR], was synthesized in a single step as a lithium salt. It was then reacted with a series of first-row transition metal(II) halides, with widely varying results. Upon reaction with chromium, manganese, iron, or cobalt(II) chloride, dimeric complexes of the form M2(OR)4Li2Cl2 were formed, which displayed rare seesaw geometry at the metal. This unusual geometry was confirmed by various spectroscopic and computational studies. Computational studies also indicate that the steric bulk of the ligand, as well as the inclusion of lithium atoms in the molecules, are what lead to the seesaw geometry. Reaction of …

Electron Transfer Studies In Langmuir-Blodgett Films Of Metallosurfactants For Current Rectification, Corrosion Mitigation, And Water Oxidation, Sunalee Gonawala Jayasundara Mudiyanselage

Wayne State University Dissertations

The work presented in this dissertation is focused on the design and synthesis of new redox-active amphiphilic architectures to optimize and understand the redox, electronic, and film formation properties for applications in current rectification, corrosion mitigation, and water oxidation. As such, new redox-active, and amphiphilic iron(III), cobalt(III), nickel(II), copper(II), and zinc(II) complexes were synthesized as precursors for Langmuir-Blodgett films used for the aforementioned applications.

For the use in molecular rectification, amphiphilic copper(II) and nickel(II) complexes with [N2O2] ligand environment were synthesized. Homogeneous film formation ability was observed between ~20-25 mN/m pressure, with a film collapse observed at ~35 mN/m for …

Synthesis And Heteroallene Reactivity Of Bis(Aldimino)Pyridine Nickel Complexes In Four Different Oxidation States, Blake Reed

Wayne State University Dissertations

A series of redox non-innocent bis(aldimino)pyridine ligands were synthesized. These were then reacted with nickel(II) salts to form Ni[NNN]X2 complexes. Cyclic voltammograms of these nickel(II) complexes suggest that more reduced states can be achieved. Reduction of these nickel(II) complexes lead to distorted square planar complexes with the halide bent ~20° out of the plane. EPR suggests that spin density is located on the metal as g-values of >2.01 were obtained. This differs from previously reported analogous bis(ketimino)pyridine complexes, which show a ligand-based radical and nickel(II). DFT confirms that as the Npyr-Ni-X angle decreases, spin density on the nickel increases. Because …

Europium(Ii)-Containing Complexes For Responsive Magnetic Resonance Imaging, Levi Alexander Ekanger

Wayne State University Dissertations

The research projects described in this dissertation are focused on studying the oxidation of EuII-containing complexes within the context of responsive MRI. Prior to this research, EuII had not been explored within the context of oxidation-responsive MRI nor had the use of this ion been reported in vivo. The results of these studies enable predictions about the oxidation-responsive behavior of EuII-containing complexes in vitro and in vivo.

The EuII-containing cryptate 1.33 was used to evaluate EuII-based positive contrast enhancement after intravenous, intraperitoneal, and subcutaneous injections. The transitory behavior of the positive contrast enhancement correlated with reported levels of oxygenation and …

The Dawn Of New Quantum Dots: Synthesis And Characterization Of Ge1-Xsnx Nanocrystals For Tunable Bandgaps., Richard J. Esteves

Theses and Dissertations

Ge_1-xSn_x alloys are among a small class of benign semiconductors with composition tunable bandgaps in the near-infrared spectrum. As the amount of Sn is increased the band energy decreases and a transition from indirect to direct band structure occurs. Hence, they are prime candidates for fabrication of Si-compatible electronic and photonic devices, field effect transistors, and novel charge storage device applications. Success has been achieved with the growth of Ge_1-xSn_x thin film alloys with Sn compositions up to 34%. However, the synthesis of nanocrystalline alloys has proven difficult due to larger discrepancies (~14%) in …

Fabrication Of Multifunctional Nanostructured Porous Materials, Ahmed A. Farghaly

Theses and Dissertations

Nanostructured porous materials generally, and nanoporous noble metals specifically, have received considerable attention due to their superior chemical and physical properties over nanoparticles and bulk counterparts. This dissertation work aims to develop well-established strategies for the preparation of multifunctional nanostructured porous materials based on the combination of inorganic-chemistry, organic-chemistry and electrochemistry. The preparation strategies involved one or more of the following processes: sol-gel synthesis, co-electrodeposition, metal ions reduction, electropolymerization and dealloying or chemical etching. The study did not stop at the preparation limits but extended to investigate the reaction mechanism behind the formation of these multifunctional nanoporous structures in order …

Electronic Structure And Stability Of Ligated Superatoms And Bimetallic Clusters, William H. Blades

Theses and Dissertations

Quantum confinement in small metal clusters leads to a bunching of states into electronic shells reminiscent of shells in atoms. The addition of ligands can tune the valence electron count and electron distribution in metal clusters. A combined experimental and theoretical study of the reactivity of methanol with Al_nI_m⁻ clusters reveals that ligands can enhance the stability of clusters. In some cases the electronegative ligand may perturb the charge density of the metallic core generating active sites that can lead to the etching of the cluster. Also, an investigation is conducted to understand how the bonding …

A Guided Inquiry-Based Laboratory Experiment: Synthesis And Characterization Of Various Phthiocol Complexes, Turina Jangula

The Journal of Undergraduate Research

Despite proven effectiveness of constructivist guided-inquiry based instruction for college chemistry courses, teaching in advanced chemistry courses such as inorganic chemistry remains very much traditional. This persistence of traditional instructional approaches could be attributed to the lack of inquiry-based curriculum materials for these courses. In this paper a guided-inquiry based inorganic laboratory experiment on the synthesis and characterization of phthiocol complexes with four different metals is presented along with suggestions for implementation as a laboratory activity. The experiment is unique in terms of its development based on a social constructivist framework and has student discussion and conceptual understanding of inorganic …

Ceria Based Catalysts For Low Temperature NoX Storage And Release, Samantha Jones

Theses and Dissertations--Chemistry

Model ceria catalysts were evaluated for NOx storage and desorption performance under lean conditions. Three different storage temperatures (80 °C, 120 °C, and 160 °C) were utilized to evaluate NO_x storage. Higher temperatures resulted in higher NO_x storage. It was observed that storage of platinum promoted ceria resulted in higher NO_x storage compared to promotion with palladium. NO_x desorption behavior of platinum promoted ceria indicated that the majority of NO_x is released at high temperatures (> 350 °C), comparatively palladium promotion released more of the stored NO_x at lower temperatures. Diffuse Reflectance Infrared Fourier …

Decarbonylative Cross Coupling Of Phthalimides With Diorganozinc Reagents—Efforts Toward Catalysis, Kimberly S. Deglopper, Sarah K. Fodor, Thomas Bd Endean, Jeffrey B. Johnson

Faculty Publications

The decarbonylative coupling of phthalimides with diorganozinc reagents to form o-substituted benzamides has been previously demonstrated as a viable process, but only with stoichiometric nickel(0). Investigations into a number of reaction variables, including solvent, ligand, and substrate substitution, have yielded multiple sets of conditions capable of achieving up to 10 catalyst turnovers, most successfully with the use of electron withdrawing nitrogen substituents on the phthalimide. In addition, these investigations have provided insight into the intermediates within the catalytic cycle and have revealed new approaches to the development of a general catalytic methodology.

Gravimetrically Characterizable Common Alkali Reducing Agents And Ligand Design Of A New Electron Rich Guanidinate, Efrain Maximiliano Castillo

Open Access Theses & Dissertations

SynThesis, isolation and characterization of 12 new alkali arenides was performed by the addition of the chelating base 18-crown-6. Electrochemistry, UV-vis/NIR spectroscopy and XRD studies were performed.

The incoorporation of an imidazolin-2-iminato group to the background of a guanidinate showed that this kind of ligand is electronically flexible and metal dependent. It was found that is more electron donating than some previously reported guanidinates and ketimine guanidinates.

Conversion Of Crude Glycerol Using Clostridium Pasteurianum Into Butanol, Stephen Morgan

Summer Community of Scholars Posters (RCEU and HCR Combined Programs)

No abstract provided.

Non-Conventional Approaches To Syntheses Of Ferromagnetic Nanomaterials, Dustin M. Clifford

Theses and Dissertations

The work of this dissertation is centered on two non-conventional synthetic approaches to ferromagnetic nanomaterials: high-throughput experimentation (HTE) (polyol process) and continuous flow (CF) synthesis (aqueous reduction and the polyol process). HTE was performed to investigate phase control between Fe_xCo_1-x and Co_3-xFe_xO_y. Exploration of synthesis limitations based on magnetic properties was achieved by reproducing M_s=210 emu/g. Morphological control of Fe_xCo_1-x alloy was achieved by formation of linear chains using an H_ext. The final study of the Fe_xCo_1-x chains used DoE to …

Sol-Gel Assembly Of Metal Nanostructures Into Metallic Gel Frameworks And Their Applications, Xiaonan Gao

Theses and Dissertations

The advent of nanoscience and nanotechnology has sparked many research forefronts in the creation of materials with control over size, shape, composition, and surface properties.^1,2 However, for most of the applications, nanoscale materials need to be assembled into functional nanostructures that exhibit useful and controllable physical properties. Therefore, numerous efforts on the assembly of nanoparticles (NPs) using organic ligands, polymers and polyelectrolytes have been reported.^3,4 However, the interactions between NPs are mediated by intervening ligands, which are detrimental to charge transport and limit the thermal stability. Hence, developing a new method to produce solid …

The Optimization Of The Synthesis And Characterization Of Vapor-Liquid-Solid Grown Zno Nanowires, Silas R. Fiefhaus

Theses and Dissertations--Chemistry

ZnO nanowires are a promising material with great semiconductor properties. ZnO nanowires were prepared by carbothermal reduction and vapor-liquid-solid growth mechanism. Altering a variety of parameters ranging from mole to mole ratio of ZnO to C all the way to gas flow rate was examined. The nanowires were then characterized and their morphology examined under a SEM to observe what effect the parameter had on the morphology of the nanowires. From the experiments and the parameters tested it was observed that in order to produce the highest quality straight nanowires one should use a mole to mole ratio of ZnO …

Organometallic Materials: Ferroceno[C]Thiophenes And 1,2-Bisthienylmetallocenes, Surya R. Banks

Theses and Dissertations--Chemistry

Development of synthetic routes toward two general organometallic frameworks was undertaken. The first project involved synthetic attempts of substituted and unsubstituted ferroceno[c]thiophene while the second one was the synthesis of 1,2-dithienylmetallocenes. The long-term goal of this work is to lay the foundations for study of electronic, electrochromic, redox, and optical properties of thiophene-based materials integrated with organometallic systems such as ferrocene, ruthenocene and cymantrene. The synthetic pathway for the target molecule in the first project involved converting 1,2-bis(hydroxymethyl)ferrocene to 1,2-bis(thiouroniummethyl)ferrocene with thiourea under acidic conditions. Refluxing the salt in base followed by acidification resulted in 1,2-bis(mercaptomethyl)ferrocene, which is …

Design, Synthesis And Physicochemical Analysis Of Ruthenium(Ii) Polypyridyl Complexes For Application In Phototherapy And Nucleic Acid Sensing, Erin Melissa Wachter

Theses and Dissertations--Chemistry

Current chemotherapeutics exhibit debilitating side effects as a result of their toxicity to healthy tissues. Reducing these side effects by developing chemotherapeutics with selectivity for cancer cells is an active area of research. Phototherapy is one promising modality for selective treatment, where drug molecules are “turned on” when irradiated with light, reducing damage to healthy tissues by spatially restricting the areas exposed to irradiation. A second approach to improve selectivity is to exploit the differences in cancerous versus healthy cells, such as increased metabolism and/or upregulation of cell surface receptors. Ruthenium(II) polypyridyl complexes are candidates for phototherapy due to their …