Physical Sciences and Mathematics Commons^™

Dynamic Metal-Ligand Interactions In Semiconducting Π-Conjugated Materials, Peter Blake Joseph St Onge

Electronic Theses and Dissertations

Over the years, the development of materials has seen a vast amount of expansion into a variety of disciplines which have demonstrated usefulness in a large span of applications. One of these new and developing themes is the use of metals and ligands which are incorporated into polymers to modify their properties, which can enable different desired properties. Incorporation of metal-ligand complexes in materials chemistry has proven to be an area of rising interest, however, many of these interactions and systems remained completely unexplored. Understanding the key fundamental principles of how these materials can be changed and modified through metal-ligand …

Inorganic Chemical Reasoning Skills: An Exploratory Study Into Understanding Students’ Choices And Thought Processes, Hannah P. Thompson

MSU Graduate Theses

Predicting the products of reactions is a fundamental skill for practicing inorganic chemists. However, the current knowledge of the strategies that students use to solve them is limited. Presumably, instructors of inorganic chemistry courses give complete-the-reaction assessment items hoping that students will use their knowledge of inorganic concepts to solve them; but it is conceivable that a successful student could use heuristics or domain general problem-solving methods. I proposed this study to determine which strategies were used by students when solving complete-the-reaction tasks in inorganic chemistry, and also to make qualitative connections between strategy and accuracy. This was done in …

Progress Towards Synthesis And Characterization Of Bay-Annulated Indigo Chromophores, Katherine Weiss, Denise Femia

HON499 projects

Through acetylation, N,N’-diacetylindigo was synthesized from indigo. N,N’-diacetylindigo and 2-thiopheneacetyl chloride were combined in an attempt to synthesize 7-thiophenyl bayannulated indigo (BAI). After 1H NMR characterization, it was found that the product was not 7-thiophenyl BAI. A previously synthesized sample of 7-phenyl BAI was purified. UV-VIS absorbance, fluorescence, IR, and 1H NMR were used to characterize the compounds.

Continuing The Metalation And Ring Closure Of Biliazine, Joshua Villers

Williams Honors College, Honors Research Projects

Continuing previous research conducted by Dr. Ziegler and his Graduate Students in which different metals were selected to metalate the compound Biliazine as well as finding metals that could be used to close the ring system in Biliazine.

Assessing The Robustness And Versatility Of Nanojars For Anion Binding, Mia Lily Ann Jawor

Masters Theses

Supramolecular chemistry is a field in chemistry that focuses on intermolecular bonds in a “host-guest complex” or supramolecular assemblies. Nanojars are supramolecular assemblies of the formula [anion⊂{Cu(μ-OH)(μ-pz)}_n] (n = 27‒33) which incarcerate kosmotropic anions, such as carbonate (CO₃^2‒), sulfate (SO₄^2‒) and hydrogen phosphate (HPO₄^2‒). Nanojars consist of three [Cu(μ-OH)(μ-pz)]_x (x = 6‒14, except 11) rings that are assembled similarly to Matryoshka dolls, where the top and bottom rings act as guests for the central ring. The larger central ring is bound to the two smaller rings by multiple …

Sustained Release Of Persulfate And Iron(Ii) Ions From Inert Inorganic Materials For Groundwater Remediation, Peter Pham

Masters Theses

Contamination of groundwater, initiated from years of human negligence, continues to persist despite major advancements in water remediation technologies. The generated groundwater plumes can continuously replenish contaminants such as dense nonaqueous phase liquids (DNAPLs) through the aid of slow-moving water. Thus, long-term treatment of this flow system has proven to be problematic. A selection of sophisticated sustained diffusion technologies is needed to help prevent further damage to this prominent freshwater source.

Here, a novel in-situ chemical oxidation (ISCO) method was designed to incorporate persulfate into silica mediums such as zeolite, diatom, and silica flour for the treatment of groundwater contaminants …

Solvent-Free Synthesis Of Metal Coordination Compounds Using Ball Mills, Jenna Cantway

Masters Theses & Specialist Projects

Mechanochemistry utilizes mechanical energy to promote chemical reactions to completion. Samples ground with a ball mill are placed under consistent pressure and temperature, which allows for increased surface area, shorter reaction times and overall better control of reaction conditions compared to the use of a mortar and pestle. Many synthetic techniques to prepare metal coordination compounds use a solvent. The solvent promotes the reactions by providing a route for reagents to interact. While solvents facilitate reactions, there is interest in reducing or eliminating solvents altogether during the synthesis process due to potential instability of a solvent under certain experimental conditions …

Leaving Ligand Effects On Reactivity And Solubility Of Monofunctional Platinum(Ii) Anticancer Complexes, Heidi Linn Hruska Millay

Masters Theses & Specialist Projects

Monofunctional platinum(II) complexes, such as phenanthriplatin and pyriplatin, have notably different characteristics from the bifunctional anticancer complexes, such as cisplatin and oxaliplatin, which have detrimental toxicities and resistance associated with them. The unique properties of the monofunctional complexes may be exploited to target cancer cells without producing the toxic side effects associated with the current FDA-approved platinum-based anticancer drugs. To advance the understanding of these monofunctional platinum(II) complexes, this study replaced the chloride leaving ligand with an acetate group, which should increase solubility and alter the rate of reactivity with key amino acid and nucleotide targets. Phenanthriplatin and pyriplatin compounds …

Steric Effects On The Formation Of Manganese Oxide Clusters And 2-Dimensional Ammonium Formate Architectures, Carl Oberle

Dissertations

It has been demonstrated by the Beatty group that altering the identity of the ortho-substituent of a dianiline counterion affects the assembly and dimensionality of a cadmium-chloride layer from 2-D to 0-D. This work seeks to extend this finding to metal oxide and organic hydrogen-bonded materials. By systematically increasing the ortho­-substituent’s size on the benzoate building block of reported manganese oxide clusters, of formula Mn_xO_y(O₂C-R)_zL_w (where R = Alkyl, L = neutral monodentate ligand), we aim to impact the self-assembly of these materials relative to their parent …

Inorganic Nanocrystals And Their Applications In Hybrid 0d:2d Material Optoelectronics, Mathew Kelley

Theses and Dissertations

Functional nanomaterials have garnered great interest as candidates for use in next-generational optoelectronics such as solar photovoltaics, light-emitting diodes, and photodetectors. Among these low-dimensional materials, hybrid devices employing both 0D and 2D materials are of interest due to exploitation of the favorable characteristics of each component, and performances superior to standalone counterparts are achievable. This thesis is divided into two parts, as follows. The first two chapters will introduce lowdimensional materials and their favorable characteristics; our work on the formation of ligand-exchanged nanocrystal thin films purified by gel-permeation chromatography will also be discussed. In the second component, the formation and …

Bimetallic Complexes: The Fundamental Aspects Of Metal-Metal Interactions, Ligand Sterics And Application, Michael Bernard Pastor

University of the Pacific Theses and Dissertations

Metal containing complexes have been used to catalyze various organic transformations for the past few decades. The success of several mononuclear catalysts led to transition metal catalysts used in pharmaceuticals, environmental, and industrial processes. While mononuclear complexes have been used extensively, bimetallic systems have received far less attention. Bimetallic or polynuclear sites are commonly found in metalloenzymes that perform elegant transformation in biological systems, underlying their significance. Inorganic chemists take inspiration from nature and design model bimetallic complexes to further study this cooperativity effect. A bimetallic platform offers many structural and functional differences such as the identity of the metal …

Metal Oxyhalides And Halides For Use As Electrode Materials In Li-Ion Batteries, Jonathan Mark Powell

Doctoral Dissertations

Synthesis of select metal halides and oxyhalides are explored in the form of direct fluorination using a fluidized bed reactor system, direct chlorination using hydrogen chloride gas, and a degradation dehydration reaction as novel methods towards the synthesis of these select metal halides and oxyhalides. The flexibility of the direct fluorination technique is demonstrated by the ability to vary the degree of fluorination based on the reaction conditions of temperature, time, and fluorine concentration. Conversion electrodes in the form of metal halides and metal oxyhalides are investigated as both anode and cathode materials for lithium ion batteries. The resulting electrochemical …

Cadmium Chloride Dimensionality Changes From Ortho-Substituted Anilines, Stephanie Cernicek

Dissertations

Inorganic-organic hybrid metal halide materials have been of great interest recently due to the useful properties offered by such a combination. The inorganic portions usually consisting of MX₆^2- subunits, (M = Pb, Sn, Cd, Cu; X = Cl, Br, I) most often form 2-D perovskite layers where the metals are bridged by corner sharing halides. The organic portion, usually consisting of primary amines or anilines provides a template for the inorganic framework and in some cases, dictates the dimensionality (2-D, 1-D, 0-D) of the network. These materials have various applications in host-guest chemistry catalysis, and gas storage, or …

Controlled Synthesis And Utilization Of Metal And Oxide Hybrid Nanoparticles, Cameron Cowgur Crane

Graduate Theses and Dissertations

This dissertation reports the development of synthetic methods concerning rationally-designed, hybrid, and multifunctional nanomaterials. These methods are based on a wet chemical, solution phase approach that utilizes the knowledge of synthetic organic and inorganic chemistry to generate building blocks in solution for the growth of nanocrystals and hybrid nanostructures. This work builds on the prior knowledge of shape-controlled synthesis of noble metal nanocrystals and expands into the challenging realm of the more reactive first row transition metals. Specifically, a microemulsion sol-gel method was developed to synthesize Au-SiO2 dimers as precursors for the synthesis of segmented heterostructures of noble metals that …

The Synthesis And Characterization Of Photoluminescent Conjugated Frameworks Containing Silicon And Germanium, Douglas William Hammerstroem

Dissertations

Siloles and 9-heterofluorenes (Si, Ge) are conjugated π-electron systems containing Group 14 atoms which demonstrate unique properties such as high electron affinity, mobility, and bathochromically shifted optical spectra relative to their all-carbon analogs. This is due to their low-lying lowest-unoccupied molecular orbital (LUMO) which is resultant of the σ*-π* conjugation between the exocyclic groups at the Group 14 center and the butadiene unit of the ring. As a consequence, they have received considerable attention for their use as components for a wide variety of optical and electronic applications such as organic light emitting diodes (OLEDs), photovoltaic devices, field-effect transistors (FETs), …

Electrochemistry And Spectroscopy Of A Molybdenum Porphyrin Compound, Jay S. Bhanot, Kyle A. Grice

DePaul Discoveries

Carbon dioxide has been a problematic greenhouse gas since the beginning of the industrial age. In an effort to remediate its effects on the climate, multiple techniques have been utilized in the chemical and electrochemical reduction of CO₂. Homogeneous electrocatalysis for carbon dioxide reduction has been a topic of increasing interest. However, a full examination of the catalytic performance of early transition metals supported by macroligands has yet to be done. The research reported involves synthesis of a chelate of molybdenum within a tetraphenylporphyrin, and then synthesis, purification, and characterization of its ability to reduce carbon dioxide. The …

Synthesis Of Dinucleating Ligands And Their Dinuclear Metal Complxes:Applications In Sensing And Small Molecule Activation, Jeffrey William Beattie

Wayne State University Dissertations

Dinuclear metal complexes provide a route to interesting structure and reactivity. Two common uses of dinuclear metal complexes are sensing and activation of small molecules. Herein we describe a series of dinuclear metal complexes capable of sensing of oxalate and activation of carbon disulfide.

Sensing of oxalate is of great interest because high oxalate concentration (hypooxaluria) is a major cause of kidney stones. Dinuclear metal complexes can act as sensors for oxalate because the oxalate can bridge between the metal centers. Herein we describe a colorimetric oxalate sensor capable of regeneration. Upon addition of oxalate to a pink solution of …

Exploration Of Bimetallic Nickel And Cobalt Complexes For Catalytic Oxidative Cleavage Of Alkenes And Hydroformylation, Ciera Vonn Duronslet

LSU Doctoral Dissertations

The “old” bimetallic nickel complexes, meso- and rac-Ni2Cl4(et,ph-P4) were investigated as possible “catalysts” for the oxidative cleavage of alkenes using an unsaturated fatty acid, oleic acid, as the substrate. The “new” bimetallic nickel complexes with a stronger chelating tetraphosphine ligand, meso- and rac-Ni2Cl4(et,ph-P4-Ph), were also synthesized and tested for the oxidative cleavage of oleic acid. All four dinickel complexes were found to be active for the oxidative cleavage of oleic acid, producing extremely small amounts of aldehyde product. The Stanley research group also discovered the oxidative cleavage of alkenes using only the “old” et,ph-P4 tetraphosphine ligands with no metal centers. …

Photochemistry Of A Series Of Weakly Coupled Dinuclear Ruthenium(Ii) Complexes, Latisha Michelle Puckett

Graduate Theses and Dissertations

An improved synthetic method was developed for symmetric ruthenium(II) polypyridine complexes with the form L2Ru(diphen)RuL2. The scope of the reaction was investigated in regards to the ligands, bridging ligands, and starting materials. Several ligands were successful in the synthesis, including 2,2’-bipyridine (bpy), 4,4’-dimethyl-2,2’-dipyridyl (dmb), 1,10-phenanthroline (phen), 4,7-diphenyl-1,10-phenanthroline (dpphen), and 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen). Ligands that did not react to form symmetric dimeric complexes were 2,2’-bipyrazine, bpz, and 2,2’-bipyrimidine, bpm.

Dpp, 2,3-bis(2-pyridyl)-pyrazine, effectively replaced diphen as the bridging ligand to produce (phen)2Ru(dpp)Ru(phen)24+. However, replacing the [Ru(CO)2Cl2]n with Ru(DMSO)4Cl2 did not prove successful. The newly developed synthesis was also applied to the synthesis of …

Building An Online Teaching Community: An Evolving Tale Ofcommunication, Collaboration, Andchemistry, Barbara Reisner, Hilary Eppley, Margret Geselbracht, Elizabeth Jamieson, Adam Johnson, Sheila Smith, Joanne Stewart, Lori Watson, Scott Williams

Hilary J. Eppley

The Interactive Online Network of Inorganic Chemists (IONiC) has grown from a small group of faculty to a national and international network focused on improving inorganicChemistry learning. IONiC’s vision is to create a community of teachers and learners who make teaching visible using social networking tools to share, discuss, test, and assess their teaching methods. The features that have allowed the IONiC community to develop and grow and IONiC’s vision for the future are described. It is likely that the lessons learned apply to other groups seeking to develop professional communities through social networking.

Ionic: A Cyber-Enabled Community Of Practice For Improving Inorganic Chemicaleducation, Hilary Eppley, Adam Johnson, Ethan Benatan, Margret Geselbracht, Joanne Stewart, Barbara Reisner, Lori Watson, B. Williams

Hilary J. Eppley

IONiC’s purpose is to enhance the inorganicChemistry classroom and laboratory experience for students and faculty members through the development of a vibrant virtual “community of practice”.

Jce Viper: An Inorganic Teaching And Learning Community, Ethan Benatan, Jezmynne Dene, Hilary Eppley, Margret Gesebracht, Elizabeth Jamieson, Adam Johnson, Barbara Reisner, Joanne Stewart, Lori Watson, B. Williams

Hilary J. Eppley

To facilitate the effective sharing of teaching tools among faculty and the development of deep subject knowledge in support of teaching, a group of faculty from predominantly undergraduate institutions has established a virtual community of inorganic chemists, IONiC (Interactive Online Network of Inorganic Chemists). Our mission is to enhance the inorganicChemistry classroom and laboratory experience for students and faculty members through the development of a vibrant, collaborative, and open community. VIPEr, the Virtual Inorganic Pedagogical Electronic Resource, is a Web site that forms the online home for our community. VIPEr is an interactive Web resource that combines a repository of …

Isoquinoline-Derivatized Tris(2-Pyridylmethyl)Amines As Fluorescent Zinc Sensors With Strict Zn2+/Cd2+ Selectivity, Shawn Burdette, Yuji Mikata, Keiko Kawata, Saaya Takeuchi, Kaori Nakanishi, Hideo Konno, Saori Itami, Keiko Yasuda, Satoshi Tamotsu

Shawn C. Burdette

Tris(2-pyridylmethyl)amine-based fluorescent ligands, N,N-bis(1-isoquinolylmethyl)-2-pyridylmethylamine (1-isoBQPA) and N,N-bis(7-methoxy-1-isoquinolylmethyl)-2-pyridylmethylamine (7-MeO-1-isoBQPA), have been prepared and the Zn2+-induced fluorescence enhancement has been investigated. Upon excitation at 324 nm, 1-isoBQPA exhibits a very weak emission (ϕ = [similar]0.010) in DMF–H2O (1 : 1). Upon Zn2+ addition, the 1-isoBQPA fluorescence increases (ϕZn = 0.055) at 357 nm and 464 nm. The fluorescence enhancement at longer wavelengths is Zn2+-specific, whereas Cd2+ induces a small emission increase at 464 nm (ICd/I0 = 1.1, ICd/IZn = 14%). The Zn2+/Cd2+ selectivity of the fluorescent response correlates with the Cd–Nisoquinoline and Zn–Nisoquinoline bond distances measured in the crystal structures. Introduction of …

Bis(2-Quinolylmethyl)Ethylenediaminediacetic Acids (Bqendas), Tqen–Edta Hybrid Molecules As Fluorescent Zinc Sensors, Shawn Burdette, Yju Mikata, Saaya Takeuchi, Hideo Konno, Satoshi Iwatsuki, Sakiko Akaji, Ikuko Hamagami, Masato Aoyama, Keiko Yasuda, Satoshi Tamotsu

Shawn C. Burdette

Molecular hybrids of TQEN (N,N,N′,N′-tetrakis(2-quinolylmethyl)ethylenediamine) and EDTA (ethylenediamine-N,N,N′,N′-tetraacetic acid) were examined as fluorescent Zn2+ sensors. Upon the addition of Zn2+, N,N-BQENDA (N,N-bis(2-quinolylmethyl)ethylenediamine-N′,N′-diacetic acid, 1a) exhibits a 30-fold emission enhancement at 456 nm (λex = 315 nm, ϕZn = 0.018) in buffer (HEPES, pH = 7.5, 100 mM KCl). The fluorescence enhancement is Zn2+-specific as Cd2+ induces much smaller increases (ICd/I0 = 5 and ICd/IZn = 16%). These spectroscopic properties, as well as the excellent water-solubility, represent a significant improvement compared to the parent TQEN sensor (ϕZn = 0.007, ICd/IZn = 64%). The isoquinoline analog N,N-1-isoBQENDA (N,N-bis(1-isoquinolylmethyl)ethylenediamine-N′,N′-diacetic acid, 1b) possesses a …

Quantifying Factors That Influence Metal Ion Release In Photocaged Complexes Using Zincast Derivatives, Shawn Burdette

Shawn C. Burdette

Two generations of nitrobenzhydrol-based photocages for Zn2+ have been prepared and characterized. The first series includes the tridentate ZinCast-1 utilizes a bis-pyridin-2-ylmethyl-aniline ligand that forms a 5,5-chelate ring upon metal binding. The related photocages ZinCast-2 with a N-[2-(pyridine-2-yl)ethyl]-N-(pyridine-2-ylmethyl)aniline (5,6-chelate ring) and ZinCast-3 with a N,N-bis[2-(pyridine-2-yl)ethyl]aniline (6,6-chelate ring) were synthesized for comparative studies. The complexes formed by the ions Cu2+, Zn2+ and Cd2+ with three ZinCast and their photoproducts (ZinUnc) were interrogated by UV-Vis spectroscopy. The studies indicate that ZinCast-1 forms complexes of the highest stability and ZinCast-3 exhibits the most significant changes in metal affinity upon uncaging. These results suggest …

Coordination Chemistry Of Tetra(Pyrazolyl)-Lutidine Ligands And Derivatives, Tyler James Morin

Dissertations (1934 -)

There is current interest in the coordination chemistry of simple AE4 pentadentate ligands that occupy one axial (A) and four equatorial (E) positions about a given transition metal center considering that systems capable of mediating spectacular organic transformations such as alkane oxidation have been identified. The discovery of new systems will improve understanding of C-H bond activation processes which is critical to help make more efficient use of the currently diminishing fossil fuel supplies. As such, a new pentadentate ligand α,α,α',α'-tetra(pyrazolyl)lutidine (pz4lut) and its derivatives pz4,4lut, (pz4, = 4-methylpyrazole); pz*4lut, (pz* = 3,5-dimethylpyrazole); pzDIP4lut, (pzDIP = 3,5-diisopropylpyrazole) have been synthesized …

Ferrinaphth: A Fluorescent Chemodosimeter For Redox Active Metal Ions, Shawn Burdette, Randy Jackson, Yu Shi, Xudong Yao

Shawn C. Burdette

FerriNaphth, a fluorescent chemodosimeter for FeIII, has been prepared and characterized. The probe consists of a catechol ligand linked to a naphthalimide fluorophore by an aniline nitrogen linker. Upon exposure to FeIII, the aminocatechol of FerriNaphth is oxidized to the corresponding quinone, which in its imine-one tautomer, is hydrolyzed to liberate a fluorescent aminonaphthalimide derivative. The fluorescence behavior is consistent with oxidation being promoted by metal coordination.

Electronic Structural Investigations Of Bi- And Polymetallic Complexes Using Quantum Mechanical Methods, Zakiya Sheni Wilson

LSU Doctoral Dissertations

Understanding the dynamics influencing chemical reactivity is essential for properly exploiting matter into more useful purposes. In that manner, computational chemistry is a tool frequently used to study chemical properties at the most intimate level, i.e. the single molecule.

With this work, we probe the chemistry governing a variety of multi-faceted bi- and polymetallic compounds. To date our research consists of four major projects: bimetallic rhodium-catalyzed hydroformylation and aldehyde-water shift hydrocarboxylation catalysis; a novel linear M-H-M interaction in a bridged bis(dialkylphosphino)methane complex of nickel; and CeBe₁₃, a heavy fermion conductor. Computational investigations on these systems allow us to …