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Design, Synthesis and Screening of Homoleptic and Heteroleptic Platinum(ii) Pyridylazolate Complexes for N-type Semiconducting and Light-emitting Devices

Description: A series of heteroleptic and homoleptic platinum(II) complexes has been synthesized and characterized towards their use in thin film devices such as organic light-emitting diodes (OLEDs) and organic thin film transistors (OTFTs). Pyridylpyrazolate- and pyridyltetrazolate-containing ligands were selected due to their structural rigidity and ease of functionalization. Single-crystal x-ray diffraction studies of two selected heteroleptic complexes show strong aggregation with preferential stacking into vertical columns with a varying degree of overlap of the neighboring square planar molecular units. It is shown that the close proximity of the molecules to one another in the stack increases semiconducting character, phosphorescence quantum yields, and shorter radiative lifetimes. The potential for these materials towards incorporation into high-efficiency doping free white OLEDs (DFW-OLEDs) for solid-state lighting and display applications has been realized and will be expanded upon by present and future embodiments of materials in this thesis.
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Date: August 2012
Creator: Oswald, Iain William Herbert

Group 10 Catalyzed Olefin Hydroarylation

Description: Alkyl-arenes are important industry feedstock chemicals that are used as solvents, pharmaceutical precursors, and polymer monomer units. One alkyl-arene, ethylbenzene, is the main focus of this dissertation, and is produced in the million ton a year scale. As alkyl-arenes are important commodity chemicals, catalytic olefin hydroarylation is a lucrative alternative for their production rather than Friedel-Crafts alkylation or various coupling reactions that have lower atom economy, require strong acids, or are energetically demanding. Currently catalytic olefin hydroarylation still suffers from decomposition pathways of the active catalytic complexes, side reactions that lead to waste products, and unfavorable activation barriers, which represent high temperature and pressure. Modifications to the catalytically active system bipyridine platinum(II) (bpyPtII), through computational methods, are explored herein. The work presented here investigates catalytic olefin hydroarylation in order to mitigate the aforementioned difficulties. Included in this study are changes to the electronic profile of the supporting ligand, bpy, through the addition of electron withdrawing or electron donating R groups (methoxy, nitro), definite ligand replacements such as bpy to hydridotris(pyrazolyl)borate (Tp), changes in metal oxidation (II to IV), and replacing the metal center from Pt to Ni. Nickel was selected as a possible alternative to platinum as it is more Earth abundant reducing the monetary requirement for the catalyst. In addition to having a different catalytic energetic profile from platinum. Ni as expected could only facilitate single step hydrogen atom transfers due to its inability to access higher oxidations states.
Date: December 2012
Creator: Gonzalez, Hector Emanuel

The Mechanisms of Human Glutathione Synthetase and Related Non-Enyzmatic Catalysis

Description: Human glutathione synthetase (hGS) is a homodimeric enzymes that catalyzes the second step in the biological synthesis of glutathione, a critical cellular antioxidant. The enzyme exhibits negative cooperativity towards the γ-glutamylcysteine (γ-GC) substrate. In this type of allosteric regulation, the binding of γ-GC at one active site significantly reduces substrate affinity at a second active site over 40 Å away. The presented work explores protein-protein interactions, substrate binding, and allosteric communication through investigation of three regions of hGS: the dimer interface, the S-loop, and the E-loop. Strong electrostatic interactions across the dimer interface of hGS maintain the appropriate tertiary and quaternary enzymatic structure needed for activity. The S-loop and E-loop of hGS form walls of the active site near γ-GC, with some residues serving to bind and position the negatively cooperative substrate. These strong interactions in the active site serve as a trigger for allosteric communication, which then passes through hydrophobic interactions at the interface. A comprehensive computational and experimental approach relates hGS structure with activity and regulation. ATP-grasp enzymes, including hGS, utilize ATP in the nucleophilic attack of a carboxylic acid in a reaction thought to proceed through the formation of an acylphosphate intermediate. Small metal cations are known to chelate the terminal phosphates of actives site ATP, yet the role of these atoms remains unclear. In the presented work, a computational metal substitution study establishes the role these divalent cations in the catalysis of peptide bonds. The simple model is used to determine the impact of metal cations on the thermodynamics and kinetics, an important stepping stone in understanding the importance of metal cations in larger biological systems.
Date: May 2015
Creator: Ingle, Brandall L.

Modeling Transition Metal Catalysts for Small Molecule Activation and Functionalization

Description: There is a high demand for the development of processes for the conversion of ubiquitous molecules into industrially useful commodities. Transition metal catalysts are often utilized for the activation and functionalization of small organic molecules due to their diverse nature and proven utility with a myriad of chemical transformations. The functionalization of methane (CH4) and dinitrogen (N2) to methanol (CH3OH) and ammonia (NH3) respectively is of particular interest; however, both methane and dinitrogen are essentially inert due to the inherit strength of their bonds. In this dissertation a series of computational studies is performed to better understand the fundamental chemistry behind the functionalization of methane and the activation of dinitrogen in a homogeneous environment. A catalytic cycle is proposed for the oxy-functionalization of methane to methanol. The cycle consists of two key steps: (1) C-H activation across a metal-alkoxide bond (M-OR), and (2) regeneration of the M-OR species through an oxy-insertion step utilizing external oxidants. The C-H activation step has been extensively studied; however, the latter step is not as well understood with limited examples. For this work, we focus on the oxy-insertion step starting with a class of compounds known to do C-H activation (i.e., Pt(II) systems). Computational studies have been carried out in an attempt to guide experimental collaborators to promising new systems. Thus, the majority of this dissertation is an attempt to extend transition metal mediated C-O bond forming reactions to complexes known to perform C-H activation chemistry. The last chapter involves a computational study of the homogeneous cleavage of N2 utilizing iron-?-diketiminate fragments. This reaction has been studied experimentally, however, the reactive intermediates were not isolated and the mechanism of this reaction was unknown. Density functional theory (DFT) calculations are carried out to elucidate the mechanism of the reductive cleavage of N2 via the sequential addition ...
Date: May 2013
Creator: Figg, Travis M.

Pathways for C—h Activation and Functionalization by Group 9 Metals

Description: As fossil fuel resources become more and more scarce, attention has been turned to alternative sources of fuels and energy. One promising prospect is the conversion of methane (natural gas) to methanol, which requires an initial activation of a C-H bond and subsequent formation of a C-O bond. The most well studied methodologies for both C-H activation and C-O bond formation involve oxidation of the metal center. Metal complexes with facile access to oxidation states separated by four charge units, required for two subsequent oxidations, are rare. Non-oxidative methods to perform C-H bond activation or C-O bond formation must be pursued in order for methane to methanol to become a viable strategy. In this dissertation studies on redox and non-redox methods for both C-H activation and C-O bond formation are discussed. In the early chapters C-O bond formation in the form of reductive functionalization is modeled. Polypyridine ligated rhodium complexes were studied computationally to determine the properties that would promote reductive functionalization. These principles were then tested by designing an experimental complex that could form C-O bonds. This complex was then shown to also work in acidic media, a critical aspect for product stabilization. In the later chapters, non-oxidative C-H activation is discussed with Ir complexes. Both sigma bond metathesis and concerted metalation deprotonation were investigated. For the former, the mechanism for an experimentally known complex was elucidated and for the latter the controlling factors for a proposed catalyst were explored.
Date: May 2015
Creator: Pahls, Dale R

Photochemical and Photophysical Properties of Mononuclear and Multinuclear Closed Shell D10 Coinage Metal Complexes and Their Metallo-organometallic Adducts

Description: This dissertation covers the studies of two major topics: the photochemistry of mononuclear and multinuclear gold(I) complexes and synthetic approaches to tailor photophysical properties of cyclic trinuclear d10 complexes. First a detailed photochemical examination into the photoreactivity of neutral mononuclear and multinuclear gold(I) complexes is discussed, with the aim of gold nanoparticle size and shape control for biomedical and catalysis applications. Next is a comprehensive systematic synthetic approach to tailor the photophysical properties of cyclic trinuclear d10 complexes. This synthetic approach includes an investigation of structure-luminescence relationships between cyclic trinuclear complexes, an examination into their π-acid/π-base reactivity with heavy metal cations and an exploration into the photophysical properties of new heterobimetallic cyclic trinuclear complexes. These photophysical properties inspections are used to screen materials for their employment in molecular electronic devices such as organic light-emitting diodes (OLEDs) and thin film transistors (OTFTs).
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Date: December 2013
Creator: McDougald, Roy N., Jr.

Triimine Complexes of Divalent Group 10 Metals for Use in Molecular Electronic Devices

Description: This research focused on the development of new metal triimine complexes of Pt(II), Pd(II), and Ni(II) for use in three types of molecular electronic devices: dye sensitized solar cells (DSSCs), organic light-emitting diodes (OLEDs), and organic field effect transistors (OFETs). Inorganic complexes combine many advantages of their chemical and photophysical properties and are processable on inexpensive and large area substrates for various optoelectronic applications. For DSSCs, a series of platinum (II) triimine complexes were synthesized and evaluated as dyes for nanocrystalline oxide semiconductors. Pt (II) forms four coordinate square planar complexes with various co-ligands and counterions and leads to spanning absorption across a wide range in the UV-Vis-NIR regions. When those compounds were applied to the oxide semiconductors, they led to photocurrent generation thus verifying the concept of their utility in solar cells. In the OLEDs project, a novel pyridyl-triazolate Pt(II) complex, Pt(ptp)2 was synthesized and generated breakthrough OLEDs. In the solution state, the electronic absorption and emission of the square planar structure results in metal-to-ligand charge transfer (MLCT) and an aggregation band. Tunable photoluminescence and electroluminescence colors from blue to red wavelengths have been attained upon using Pt(ptp)2 under different experimental conditions and OLED architectures. In taking advantage of these binary characteristics for both monomer and excimer emissions, cool and warm white OLEDs suitable for solid-state lighting have been fabricated. The OFETs project represented an extension of the study of pyridyl-triazolate d8 metal complexes due to their electron-transporting behavior and n-type properties. A prescreening step by using thermogravimetric calorimetry has demonstrated the stability of all three M(ptp)2 and M(ptp)2(py)2 compounds and their amenability to sublimation. Preliminary current-voltage measurements from simple diodes has achieved unidirectional current from a Pt(ptp)2 neat layer and demonstrated its n-type semiconducting behavior.
Date: August 2010
Creator: Chen, Wei-Hsuan