Inorganic Chemistry Commons^™

Nontoxic Paints Using Cornstarch As Binders, Maile Prater

Honors Projects

For this project, paints were created using different metal compounds which interacted with cornstarch and pectin to determine whether the metals would coordinate with these polysaccharides to create new types of watercolor paints. The paints that were created were ran through an RGB analysis to determine how much of each RGB color is present in a solution and then were ran through a rheometer to determine how the viscosity differed between each solution.

Integrating Multimodal Analysis For Chemical Detection In Victorian Bookcloth: Correlations, Advantages, And Limitations, Leila Ais, Abigail L. Hoermann, Jafer Aljorani

Student Scholar Symposium

The detection of heavy metals in Victorian textiles presents a set of unique analytical challenges that cannot be addressed through usage of a single modality. Here, we detail a novel multimodal analytical approach that integrates distinct yet complementary instrumentation: inductively coupled plasma-optical emission spectroscopy (ICP-OES) offering precise quantitative elemental analysis, portable X-ray fluorescence (pXRF) enabling rapid, affordable, and non-destructive detection, electron dispersive spectroscopy – scanning electron microscopy (EDS-SEM) mapping elemental distributions and sample topography, and X-ray diffraction (XRD) revealing crystalline structures. This comparative study highlights the strengths and limitations of each analytical technique, demonstrating how their combined use provides a …

Exploring Halogen Bonding Interactions In Cocrystals And Deep Eutectic Solvents, Madhushi Bandara

All Dissertations

Halogen bonding is a noncovalent intermolecular interaction analogous to hydrogen bonding that occurs between an electrophile and a nucleophile. This is often observed in compounds containing heavy halogens such as iodine and bromine. When these halogens are covalently bonded to another atom or molecule, preferably to an electron-withdrawing moiety, an electrophilic region called a sigma hole is created on the halogen atom on the extension of the covalent bond.

The first study of this dissertation presents a comprehensive characterization of eight newly synthesized triiodide salts using single-crystal X-ray diffraction, powder X-ray diffraction, thermal analysis (DSC and TGA), and Raman spectroscopy. …

Synthesis Of Phenyl-Substituted Zinc Dipyrrin Photosensitizer For Carbon Dioxide Reduction, Stephen Ankomah

Electronic Theses and Dissertations

The release of CO₂ from fossil fuel combustion drives the need for its conversion into more sustainable options like CO and CH₄ via photocatalytic reduction. This process requires a catalyst, sensitizer, and electron donor. Zinc dipyrrin-based complexes are promising photosensitizers, offering an alternative to expensive, rare-metal-based systems. Most first-row transition metal dipyrrin compounds have short excited-state lifetimes due to rapid nonradiative decay, but Zn(II) dipyrrin complexes stand out. With a d¹⁰ configuration, they lack deactivating ligand field states and can access long-lived triplet states through a charge-separated intermediate. A phenyl-substituted Zn(II) dipyrrin complex was synthesized and studied using NMR to …

Studies Of Trispyrazolylborate Molybdenum-Oxo Compounds And Related Reactions, Miranda Sanders

Graduate Theses and Dissertations

This dissertation details the design, development, and synthesis of a molybdenum-dioxo complex bearing a trispyrazolylborate ligand. The system was tested for its efficiency as a catalyst for deoxydehydration with a small substrate scope. Deoxydehydration reactions with 1-phenyl-1,2-ethanediol, diethytartrate, and 1,2-octanediol show low yields with catalytic turnover only found for diethyltartrate. Electrochemical studies show well behaved PCET behavior with two distinct electron transfer events in the presence of a proton donor. Studies of two molybdenum-dioxo complexes bearing dianionic pincer ligands were conducted to expand further on systems that have been extensively studied in our lab. Deoxydehydration of glycerol by a molybdenum-dioxo …

Exploring Inorganic And Organometallic Chemistry, W. Christopher Boyd Phd

MSL Academic Endeavors eBooks

This textbook, Exploring Inorganic and Organometallic Chemistry, covers the fundamentals of inorganic and organometallic chemistry for undergraduate and graduate students. Both theories of structure and bonding and reaction chemistry are covered, with applications to the catalysis of organic reactions, biochemistry, and drug design. A modular approach allows for basic materials of each chapter to be covered in an undergraduate course, with more advanced material suitable for M.S. and Ph.D. students."

Synthesis And Characterization Of Lanthanide Extended Structures And Their Novel Transuranic Analogues, Hunter Bernard Tisdale

Theses and Dissertations

The United States owns a substantial amount of radioactive waste as a result of decades of research, weapons manufacturing, and nuclear energy production. As nuclear energy and research continue to add to our stockpiles of waste, the issue of remediating this waste becomes more pressing. Many of the radioactive constituents of this waste, such as the transuranic (Z > 92) elements, will give off radioactivity at harmful levels for millennia. Thus, a robust method of storing this waste is paramount to ensuring public safety. Currently, nuclear waste is being processed by vitrifying it in borosilicate glass. However, this method has shortcomings …

Role Of Axial Ligation In The Conformational And Redox Properties Of Cytochromes, Morgan Elisabeth Reik

Dartmouth College Ph.D Dissertations

Heme proteins are crucial for many biological processes including respiration, transport, and catalysis. As electron carriers containing redox active metal centers, their electron transfer (ET) properties are tuned by the protein environment, wherein the reduction potential can be influenced by factors such as heme solvent accessibility, charge, the presence of neighboring redox centers, as well as the identity of the axial ligand. The axial ligand in heme proteins is especially crucial for tuning the electronic properties of the metal center, as it affects the driving force of the reaction. However, the redox properties of heme proteins are further modulated by …

Effect Of Chalcogen-Phosphorus Substituents On Enediynes Undergoing The Bergman Cyclization, Marcos Hendler, Travis Greene, Dominic A. Siriani, Carol A. Parish

Chemistry Faculty Publications

We have theoretically characterized electrocyclizations of chalcogen-phosphorus-containing enediynes. We performed quantum calculations at the BS-(U)­CCSD/cc-pVDZ level to analyze the geometries and energetics of two different cyclization pathways, each consisting of the first three chalcogens (oxygen, sulfur, and selenium). The first pathway involved the cyclization of the chalcogen-phosphorus substituents followed by Bergman cyclization, while the second pathway proceeded via Bergman cyclization followed by chalcogen-phosphorus cyclization. To more accurately understand the energies of the diradicals involved in each pathway, we also performed spin-flip characterizations using UHF reference wave functions and the spin-flip formulation of the equation-of-motion coupled cluster theory with singles and …

Time-Resolved Crystallographic Analysis Of The Mechanism Of Formation Of The Mof Hkust-1, Cody Webb Jr

Dissertations - ALL

Metal-organic frameworks (MOFs) are a class of inorganic porous coordination compounds of interest for technically relevant applications including gas storage & sequestration, catalysis, and drug delivery (Chapter 2). The last decade has seen significant development in this field of coordination chemistry, and an extensive array of MOFs have been reported despite the lack of a comprehensive scheme for how these materials form. The development of novel MOFs is not a trivial task, as the synthesis of target MOFs is notably unpredictable, and experiments require extensive trial-and-error reactions with systematic manipulation of the synthetic variables. Ideally, a toolbox method based on …

Instability Of The Octahedral Symmetry In Si8o12h8 And Ge8o12h8: A Consequence Of The Pseudo-Jahn–Teller Effect, Jules Tshishimbi Muya, Arnout Ceulemans, Carol A. Parish

Chemistry Faculty Publications

The symmetry breaking in octahedral silsesquioxane and its germanium analogues (Si8O12H8 and Ge8O12H8) has been investigated using the M06-2X/6-31++G(3df, 3pd) method and group theory. Both structures undergo  symmetry breaking, characterized by pseudo-Jahn−Teller stabilization energies of 0.22 kcal/mol for Si-POSS and 9.82 kcal/mol for Ge-POSS. Under the influence of the pseudo-Jahn–Teller effect, the distortion vector involves the vibrational a2g mode with imaginary frequency. The distortion forces in Oh-POSS are predominantly localized on the oxygen atoms and driven by the coupling between the lowest unoccupied molecular orbital (a1g) and the highest occupied molecular orbital (a2g). The symmetry breaking is attributed to a …

Epitaxial Electrodeposition Of Cu-Btc Metal-Organic Framework Thin Films Onto The (100), (110), And (111) Surfaces Of Single-Crystal Gold And Cuprous Oxide Buffer Layers, Xiaoting Zhang, John Z. Tubbesing, Jay A. Switzer

Chemistry Faculty Research & Creative Works

Metal-organic frameworks (MOFs) have well-defined pore structures. Epitaxial MOFs can produce films with uniform pore sizes and open porosity. However, the growth of epitaxial MOF thin films has remained a challenge. Herein, we demonstrate a cathodic electrodeposition method for the epitaxial growth of a well-known MOF material, copper (II)-benzene-1,3,5-tricarboxylate (Cu-BTC), from solution precursors. The epitaxial electrodeposition of Cu-BTC was achieved in a Cu (NO₃)₂-H₃BTC-H₂O₂ bath using H₂O₂ reduction to deprotonate the H₃BTC molecule. The Cu-BTC films can be grown to micrometer thicknesses with Faradaic efficiencies up …

Linking Ruthenium(Ii) Polypyridyl Complexes Into Metal-Organic Frameworks Using Iron(Ii) And Zinc(Ii), Taofeek Mayowa Ogungbade

Masters Theses & Specialist Projects

Renewable energy has attracted significant interest in recent years as society seeks to minimize its dependence on fossil fuels. Among the various strategies proposed to achieve this goal, one promising approach is the conversion of carbon dioxide into organic fuels using photocatalysts. Unlike traditional semiconductor photocatalysts, metal-organic frameworks (MOFs) offer advantages such as absorption of visible light, tunable structures, and uniform pore sizes, which enhance their efficiency in the photocatalytic reduction of carbon dioxide.

In this thesis, we report the synthesis, structure, and properties of two novel heteronuclear MOFs that incorporate ruthenium(II) complexes and 3d-block transition metals using 2,2’-bipyridine-5,5’-dicarboxylic acid …

Mechanochemical Investigation Of The Solid-State Reduction Of Metal Oxide Species, Trevor Webster

Masters Theses & Specialist Projects

Redox reactions are commonly performed in aqueous solutions. Mechanochemistry offers an alternative route to conduct these reactions in the absence of a solvent. The current research project investigates the feasibility of performing solid-state redox reactions using mechanochemistry as a means to initiate. Utilizing a Wig-L-Bug, sodium metavanadate and vanadium(V) oxide are milled with various inorganic and organic reducing agents. Zn, Mg, Na₂SO₃, ascorbic acid, and benzoic acid were selected due to the agents’ high reduction potential and ability to reduce vanadium(V) species in acidic or basic solutions. The use of X-ray powder diffraction (XRD) and scanning …

Investigating The Influence Of Experimental Parameters On The Formation Of Gold Nanoparticles: A Green Synthesis And Design Of Experiments Approach, Isaac Opeyemi Subuloye

Master's Theses

This thesis examines the green synthesis of gold nanoparticles using catechin, a naturally occurring plant-derived compound, as both a reducing and capping agent. The synthesis process was guided by a structured Design of Experiments (DOE) methodology to ensure systematic investigation and optimization. A two-phase experimental approach was adopted. First, a full factorial screening design was used to evaluate the effects of catechin concentration, NaOH concentration, and pre-reaction time. This was followed by an optimization phase using a face-centered composite design to identify conditions that produce nanoparticles with ideal characteristics. The nanoparticles were analyzed using UV-visible spectroscopy and dynamic light scattering …

Comparative Nitrene-Transfer Chemistry To Olefins Mediated By First-Row Transition Metal Catalysts Supported By A Pyridinophane Macrocycle With N4 Ligation, Himanshu Bhatia, Lillian P. Adams, Ingrid Cordsiemon, Suraj Kumar Sahoo, Amitava Choudhury, Thomas R. Cundari, Pericles Stavropoulos

Chemistry Faculty Research & Creative Works

A 12-membered pyridinophane scaffold containing two pyridine and two tertiary amine residues is examined as a prototype ligand (^tBuN4) for supporting nitrene transfer to olefins. The known [(^tBuN4)M^II(MeCN)2]²⁺ (M = Mn, Fe, Co, and Ni) and [(^tBuN4)Cu^I(MeCN)]⁺ cations are synthesized with the hexafluorophosphate counteranion. The aziridination of para-substituted styrenes with PhI=NTs (Ts = tosyl) in various solvents proved to be high yielding for the Cu(I) and Cu(II) reagents, in contrast to the modest efficacy of all other metals. For α-substituted styrenes, aziridination is accompanied by products of aziridine …

Reactivity Of Redox-Active Carboranyl Diphosphines And Carboranyl Diphosphoniums: Metal-Free Pathways For Small Molecule Activations And Transformations, Amanda Lynn Humphries

Theses and Dissertations

Transition metal catalysis has been an integral part of synthetic chemistry for its ability to selectively activate strong substrate bonds, promoting numerous crucial transformations. Despite their utility, the precious metals that are often employed in these catalytic reactions suffer from several drawbacks (including high toxicity, low natural abundance, high costs, and low sustainability), increasing the motivation to design suitable metal-free alternatives. Towards this end, several ambiphilic main-group systems have been devised to show metal-like reactivity, such as carbenes, borylenes, and Frustrated Lewis Pairs. This manuscript will describe the ambiphilic reactivity of carborane-based phosphorus compounds, highlighting the unique metallomimetic reactivity that …

Determination Of Structure-Function Relationships In Hybrid Catalysts On Metal Oxide Supports, Joseph John Kuchta

Theses and Dissertations

Transition metal catalysis has revolutionized chemical synthesis, enabling efficient and selective transformations critical to the pharmaceutical, agricultural, and materials industries. However, traditional methods often rely on expensive, non-sustainable metals and harsh reaction conditions that generate significant waste. This dissertation explores a series of innovations aimed at bridging the gap between homogeneous and heterogeneous catalysis through the development of hybrid catalysts. These systems combine the molecular precision of homogeneous catalysts with the stability and practicality of heterogeneous supports, offering a pathway to more sustainable and scalable catalytic processes.

The first area of focus investigates nickel-based hybrid catalysts as a cost-effective and …

Colloidal Hot-Injection Synthesis Of Cubse2 Nanocrystals: Tetragonal Chalcogenide Templates For Superionic Lithiation Pathways, Yunhao Xu, Niket Powar, Kelly Zervos, Isabella Campbell, Simran Choudhary, Layan Al-Khaled, Progna Banerjee

Chemistry: Faculty Publications and Other Works

Copper boron selenides represent a previously unexplored class of materials with tetragonal structural symmetries and bonding chemistries potentially relevant to lithium-ion conduction. In this work, the first colloidal synthesis of nanocrystalline copper boron selenides is reported, enabling access to nanocrystals with reaction times shown as the synthetic knob to control composition and morphology. Copper boron selenide nanocrystals are synthetically designed as precursors for lithiation reactions aimed at probing structural evolution and ionic mobility pathways toward superionic conductors applicable as solid electrolytes in lithium-ion batteries. Postsynthetic lithiation studies under ambient conditions reveal a series of phase transformations and morphological changes, which …

2d Cuo/Rgo Nanocomposite: A Novel Architecture For Enhanced Cr(Vi) Photo-Reduction, Islam Gomaa, Nasser M. Hosny, Medhat A. Ibrahim

Nanotechnology Research Centre

he urgent need for efficient detoxification of carcinogenic hexavalent chromium (Cr(VI)) in aquatic environments has driven the development of advanced photocatalytic materials. This study presents the synthesis of 2D CuO/reduced graphene oxide (rGO) nanocomposite via probe sonication, designed to synergistically enhance the photocatalytic reduction of Cr(VI) to less toxic Cr(III). The nanocomposite was meticulously characterized using XRD, HRTEM, FESEM, XPS, and UV-Vis diffuse reflectance spectroscopy. Structural analysis confirmed the formation of CuO nanosheets (average size: 396 nm, thickness: 6 nm) integrated with rGO, where the rGO acted as an electron acceptor, mitigating charge recombination. XPS revealed Cu²⁺ in CuO and …