Chemistry Commons^™

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 …

Conformational Change In A Four-Tetrad Dna G-Quadruplex Upon Intercalation Of A Small-Molecule Ligand Pydh2, Kailey N. Martin, Gwendolyn Lam , '24, O. Reznichenko, K. E. Brunner, M. J. Zdilla, Sawyer E. Mccarthy, Liliya A. Yatsunyk

Chemistry & Biochemistry Faculty Works

G-quadruplexes (G4s) are non-canonical DNA structures implicated in a number of biological processes. Small-molecule ligands can alter stability and folding of G4s, which can potentially be exploited for therapeutic purposes. In this work, we investigate the interaction of telomeric DNA fragment from Tetrahymena thermophila (TET25, 5′-G(TTGGGG)₄-3′) with a G4 ligand PyDH2 belonging to the bisquinolinium family. When alone, TET25 adopts a mixture of three conformations, with the most abundant being a four-tetrad hybrid G4. In the presence of PyDH2, surprisingly, TET25 folds into an antiparallel chair G4, with PyDH2 intercalated between G-tetrads 2 and 3, according to our crystal structure. …

Asymmetric, Carboxy And Ester Functionalized Fluorophthalocyanines: Synthesis, Adsorption, And Reactivity, Sean J. Scally

Seton Hall University Dissertations and Theses (ETDs)

Strong electron-deficient compounds, fluorinated metal phthalocyanines (F_xPcM), exhibit enhanced photosensitizing properties, making them optimal candidates for photocatalytic studies. Perfluoroalkyl-substituted phthalocyanines are notably thermally robust materials that are chemically inert and resistant to electrophilic, nucleophilic, and radical, including reactive oxygen species (ROS) attacks. These properties can be attributed to their ‘Teflon-like’ inert organic shield that surrounds a reactive metal center, as well as their complete (x = 16, 40, 64), or almost complete (x = 48) lack of C-H bonds. Third-generation, functionalized, asymmetric phthalocyanines are of interest due to their ability to bind to oxidic supports via a carboxyl …

Trade-Off Between Limonene & Geraniol-Based Reprocessable And Non-Reprocessable Epoxy Thermosets: Role Of Aliphatic Diamines In Polymer Networks Design, Priyankkumar Kanubhai Patel

Electronic Theses & Dissertations

The growing demand for sustainable materials, driven by environmental concerns and the rapid depletion of fossil fuels, has garnered significant attention in the fabrication of bio-based epoxy thermosets as renewable alternatives to petroleum-derived thermosetting polymers. The present study focuses on the synthesis and characterization of epoxy prepolymer resins derived from limonene and geraniol via a two-step process, followed by the fabrication of thermally cross-linked flexible epoxy thermoset films using various traditional aliphatic diamine curing agents, namely 1,2-ethylenediamine (EDA), 1,4-butylenediamine (BDA), and 1,6-hexamethylenediamine (HDA). Additionally, the incorporation of cystamine, a disulfide-containing diamine, enabled the formation of a covalent adaptable network through …

Bio-Based Composites With Enhanced Mechanical Strength And Flame Retardancy, Riya Patel

Electronic Theses & Dissertations

Composites are versatile and useful in many fields, including aerospace, automotive, construction, and healthcare, due to their high mechanical strength. It is common practice to synthesize these materials using petroleum-based chemicals. Nonetheless, in the twenty-first century, scientists are more interested in using renewable resources to create composites. The greatest substitute for petroleum-based chemicals is vegetable oil. It has unsaturated double bonds that are modifiable chemically. In the present study, bio-polyol was synthesized using castor oil, an inedible vegetable oil. A ring-opening process was used to modify it and produce castor oil-based polyol. The synthesized castor oil-based polyol was characterized by …

Investigations Of The Electrochemical And Photochemical Properties Of Earth-Abundant Metal Complexes Stabilized By A Pentadentate Bipyridyl Macrocyclic Ligand, Skylar Nichols

Honors Theses

The creation of a selective and efficient catalyst for the multi-electron reduction of carbon dioxide (CO₂) into valuable chemicals or renewable fuels is a crucial research area. As the use of non-renewable fossil fuels and the associated greenhouse gas emissions, predominantly CO₂, continue to rise, the need for renewable and sustainable approaches to energy increases. To address both the need for clean energy and to reduce the accumulation of CO₂ in the atmosphere, this work will investigate the synthesis and catalytic activity of Earth-abundant transition metal-based complexes supported by a pentadentate ligand. The macrocyclic ligand 7-methyl-4,7,10-triaza-1,2(2,6)-dipyridinacycloundecaphane was successfully synthesized and …

Development Of Mixed O/S-Donor Imidazole Thione Ligands For Trivalent Lanthanide/Actinide Separations, Rhianna Wolsleger

All Dissertations

Separation of lanthanides and actinides is difficult due to their very similar size and charge. Increasing selectivity for actinides over lanthanides is possible by incorporating a softer, more polarizable donor atom into a chelating ligand, since the softer donor atom is capable of greater orbital overlap with the 5f orbitals of the actinides vs the 4f orbitals of the lanthanides. Sulfur-containing imidazole thione chelating ligands have not been investigated for this purpose but possess a resonance structure that puts significant negative charge on the sulfur, enabling it to form strong metal-sulfur bonds compared to other sulfur-containing ligands such as thioethers …

Synthesis And Characterization Of New Inorganic Materials In Different Length Scales; From Nanometer To Micrometer, Kirkland Sheriff

All Dissertations

In this dissertation there are a new series of Preyssler polyoxometalate (POM) crystalline solids created using electrochemical potential. It was found that using electrochemical potential, where nucleation and reduction occur simultaneously, was a convenient method for exploratory synthesis creating new crystalline solids in aqueous solution and at room temperature. The general structure feature reveals that Preyssler POM was covalently linked by various metals from the d and f block including Co²⁺, Ni²⁺, La³⁺, Nd³⁺, Gd³⁺ and Ho³⁺ where the POM was reduced by 2 to 4 electrons. The resulting solids …

Composition And Rich/Lean Loading-Dependent Density Measurements Of A Series Of Aqueous Ionic Amines For Co2 Capture, Claudia Nguyen

Honors Theses

As climate change worsens worldwide, there is a drive to develop more efficient and sustainable methods to mitigate its impact through carbon capture methods like carbon dioxide scrubbing. Carbon scrubbing directly captures carbon dioxide (CO2) emissions from industries or power plants before they are released into the environment. The CO2 captured can be utilized for various applications or can be stored underground. However, this method faces numerous challenges, such as the degradation of the solvent or corrosion of equipment. As a result, research has expanded to find a better medium to overcome these issues. In particular, aqueous ionic amines (AIA) …

Binary Solid/Liquid Equilibrium Of Mixtures Of Thermally Robust Salts And Molecular Compounds For Use As Heat Transfer Fluids, Jared Ridge Mathews

Honors Theses

Fossil fuels, contributors to climate change that may bear catastrophic consequences, power the entire world. The human species is almost entirely dependent on fossil fuels for energy, but other sources of renewable and environmentally friendly energy must be developed. Concentrated solar power (CSP) is a promising source of renewable energy with hampered potential—better heat transfer fluids (HTFs) are needed for it to be economically feasible. Currently, the HTFs in industrial use are predominantly either synthetic oils or nitrate-based molten salts. Synthetic oils are only stable up to 400 °C, and molten salts often have high melting temperatures, making them prone …

Development Of A Mechanochemical Synthesis For A Palladacycle: Exploring Solvent Characteristics And Reaction Kinetics, Kyle Lintzenich

Honors College Theses

Palladacycles are a class of palladium complexes that show utility in catalyzing carbon-carbon cross coupling reactions. Mechanochemistry provides a greener alternative to synthesizing these palladacycles via repeated impacts that transfer mechanical energy into the reaction mixture, promoting formation of the desired complex. Specifically, liquid assisted grinding (LAG) has proven to be a viable tradeoff to neat mechanosynthesis of adding a small amount of liquid to decrease synthesis times or improve conversion. Some liquids actively participate in the reaction in a process termed as non-innocent LAG. This work focuses on the development of a mechanosynthetic method using non-innocent LAG for a …

Hydrothermal Synthesis Of Single-Crystal Magnetic Oxides, Bhakti Patel

All Dissertations

Multifunctional materials are systems that have two or more properties of interest. Some of these features are polar axes, chirality, magnetic ions, triangular arrangements, and/or magnetically silent building blocks. Various combinations of these properties can result in chiral ferromagnetism, multiferroic magnetoelectric behavior, antiferromagnetism, and quantum spin liquids and spin ices. By tuning these structure-property relations, quantum computing, memory, and sensors may be created. Large single crystals allow for a better understanding of the magnetic behavior of these crystals since they can be oriented in a magnetic field. Inorganic single crystals have a wide range of applications but growing high-quality single …

Structure Disorder And Magnetic Behavior Of An Olivine-Type Cathode Material, Hamida Hassan, Madalynn Marshall

Symposium of Student Scholars

Our research investigates the structure disorder and magnetic behavior of Li(Mn,Fe)PO₄, an olivine-type material relevant for lithium-ion battery applications. Using single-crystal neutron diffraction at Oak Ridge National Laboratory, we precisely determined Mn and Fe occupancy, revealing a 56% Fe and 44% Mn distribution at the atomic 4c site within the Pnma space group. Additionally, we observed significant lithium site vacancies (78% occupied), influencing the material's electrochemical and magnetic properties. The varying Mn/Fe ratio affected spin reorientation transitions, shifting from antiferromagnetic alignment along the a-axis to the b-axis. Our findings provide crucial insights for optimizing olivine-based cathodes, enhancing energy …

Synthesis Of Surface Bound Ligands Through Click Chemistry For A Tethered Catalyst System Towards The Reduction Of Carbon Dioxide, Emma J. Goehner

Departmental Honors & Graduate Capstone Projects

The electrochemical reduction of carbon dioxide (CO₂) offers a promising strategy for reducing excess atmospheric CO₂ by converting it into valuable chemical products. This process can be catalyzed by transition metal complexes, particularly those with extended aromatic ligands such as terpyridines which coordinate with metals in a tridentate fashion. When tethered to an electrode, the terpyridine-metal catalyst complex allows for stable binding and reusability without the need for chemical separation to recover the catalyst. Self-assembled monolayers (SAMs) of (3-bromopropyl) phosphonic acid were formed on copper surfaces, enabling attachment of terpyridine ligands through a click reaction between a …

From Clusters To Frameworks: Synthesis, Engineering, And Application Of Sub-2-Nanometer Nanoclusters And Microporous Covalent Organic Frameworks, Melika E Kenari

Chemistry Theses and Dissertations

In this dissertation, we have investigated the complex interplay of atomic composition, structural modifications in covalent organic frameworks (COFs), and atomic-level designs in bimetallic chiral nanoclusters (NCs). By synthesizing COFs and bimetallic NCs, we elucidated how these elements govern their exceptional catalytic, optical, and electronic properties. Our work demonstrates that precise atomic adjustments, tailored pore engineering in COFs, and the strategic use of chiral ligands in NCs enable fine-tuned reactivity and stability. These advancements were applied to enhance photocatalytic performance, optimize iodine adsorption, and facilitate asymmetric A3 coupling reactions, laying a robust foundation for practical applications and future innovations in …

Salmon As An Ecological Pathway Of Contaminants Into Alaskan Food Webs, Miranda Brohman, Gretchen Roffler, Dimitri G. Giarikos, David Kerstetter, Amy C. Hirons

SECLER Data

Salmon are important fish taxa for humans and animals in hemiboreal and subarctic ecosystems. Trace elements and their marine food web bioaccumulation raises biomagnification and potential human health risk concerns. Sixteen trace element concentrations and their health risk assessments were determined in seven different tissues of two Southeast Alaska salmon species (chum, Oncorhynchus keta and pink, Oncorhynchus gorbuscha). Chum tissues had overall higher trace element concentrations compared to pink, which may be attributed to a difference of diets, generally longer-lived and spending more time in the open ocean. All kidney and liver samples exceeded the tolerable daily intake for …

Effect Of Niobium Dopant On Zno Thin Films Prepared Via The Sol–Gel Spin Coating Method, Kevin Alvin Eswar, Nur Fairuz Rostan, Maryam Mohamad, Rabiatuladawiyah Md Akhir, Rosfayanti Rasmidi, Muliyadi Guliling, Najwa Ezira Azhar, Irmaizatussyehdany Buniyamin, Mohd Firdaus Malek, Mohamad Rusop Mahmood, Husairi Fadzilah Suhaimi, Saifollah Abdullah

Makara Journal of Science

Thin films of zinc oxide (ZnO) and niobium (Nb)-doped ZnO were deposited on a glass substrate using the sol–gel spin coating method. Diethanolamine, isopropyl alcohol, and zinc acetate served as the stabilizers, solvent, and starting ma-terial, respectively. Niobium pentachloride was employed as the dopant source. Energy-dispersive X-ray analysis con-firmed Nb incorporation. Field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and ultravio-let–visible spectroscopy (UV–Vis) analyses characterized the morphology, structure, and optics of the films, respective-ly. Both films, comprising nanoparticles, were visible in FESEM. Nb doping reduced the particle size from 44.2 nm to 35.8 nm. The XRD peaks at 31.23°, …

Raw Data For Violations Of Coordination: Exploring Metastable Diborides For Energy Storage, Michael Yeung

Chemistry Department Faculty Scholarship

The ideal aeronautical solid-state fuel should possess a high density (more thrust per Newton’s Third Law), high gravimetric heat of combustion (more energy for less weight), and a high volumetric heat of combustion (more room for mission-critical items). In this work, manganese diboride (MnB2) demonstrates a high density of 5.3 g/cm3, a high gravimetric heat of combustion of 38.30 kJ/g, and the highest volumetric heat of combustion of any known fuel of 202.99 kJ /cm3. When compared to the currently used fuel in Space Shuttle rocket boosters and the Space Launch System, aluminum metal, MnB2 represents a 100% increase in …

Effect Of Pre-Adsorbed Species On High-Pressure Adsorption Of Methane In Zeolite 5a Using Grand Canonical Monte Carlo (Gcmc) Simulations, Kanhamardi Lao, Brooks D. Rabideau

Shelby Hall Graduate Research Forum Posters

Natural gas upgrading, which removes impurities from methane (CH4), is essential for industrial applications, including liquefied natural gas (LNG) production and power generation, as well as for residential use. Removing non-hydrocarbon impurities such as carbon dioxide (CO2), nitrogen (N2), and water vapor (H2O), among others, along with separating heavier hydrocarbon gases from raw natural gas, is required to achieve high- purity methane and prevent pipeline corrosion. Zeolite 5A is a microporous aluminosilicate material with a pore size of approximately 5 Å, containing sodium and calcium cations that balance the framework’s negative charge. Its structure offers high thermal stability and a …

Photocathodes From Aerobic Oxidation Of Tellurorhodamines, Amelia Jellison

Dissertations and Theses

Growing environmental concerns have facilitated an increased need for renewable energy. Solar energy is an excellent source of renewable energy, however current dye-sensitized solar cells are not efficient enough for commercial use. This thesis attempts to create a novel dye-sensitized cathode to increase the efficiency of dye-sensitized solar cells.

Dye-sensitized cathodes could lower the energy level on the cathode and thereby increase the overall efficiency of the solar cell, however until now it has not been attempted. A tellurorhodamine dye with a mesityl ring was chosen as the dye for its ability to aerobically oxidize in the presence of light. …

Interaction Of N-Methylmesoporphyrin Ix With A Hybrid Left-/Right-Handed G-Quadruplex Motif From The Promoter Of The Slc2a1 Gene, Paul Seth , '23, Eric Xing , '26, Andrew D. Hendrickson , '27, Kevin Li , '22, R. Monsen, J. B. Chaires, S. Neidle, Liliya A. Yatsunyk

Chemistry & Biochemistry Faculty Works

Left-handed G-quadruplexes (LHG4s) belong to a class of recently discovered noncanonical DNA structures under the larger umbrella of G-quadruplex DNAs (G4s). The biological relevance of these structures and their ability to be targeted with classical G4 ligands is underexplored. Here, we explore whether the putative LHG4 DNA sequence from the SLC2A1 oncogene promoter maintains its left-handed characteristics upon addition of nucleotides in the 5′- and 3′-direction from its genomic context. We also investigate whether this sequence interacts with a well-established G4 binder, N-methylmesoporphyrin IX (NMM). We employed biophysical and X-ray structural studies to address these questions. Our results indicate that …

Elucidating The Role Of The Secondary Coordination Sphere In Tuning Reactivity Of Synthetic Heme Superoxide Complexes And Other Biologically Relevant Intermediates, Garrett B. Tolbert

All ETDs from UAB

Tryptophan catabolizing human heme-dioxyganase enzymes have been linked to a multitude of disease conditions; therefore, understanding the mechanistic details of their function is of great interest to facilitate the design of effective inhibitors for therapeutic applications. Synthetic model systems have demonstrated dioxygenation of indole moieties, elucidating key mechanistic details of the overall reaction. However, the contrastingly low reactivity of the synthetic heme-superoxide intermediates compared to those of dioxygenase enzymes necessitates the revaluation of these models with direct relevance to their biological mode of action. Herein, we report detailed mechanistic studies on the reactivity of model porphyrin systems with installed non-covalent …

Transition Metal Alkoxide Complexes Synthesis Using Thallium Reagents And Design Of Iron(Ii)-Alkoxide Carbene Complexes And Their Reactivity, Lakshani Wathsala Kulathungage

Wayne State University Dissertations

ABSTRACTTRANSITION METAL ALKOXIDE COMPLEXES SYNTHESIS USING THALLIUM REAGENTS AND DESIGN OF IRON(II)-ALKOXIDE CARBENE COMPLEXES AND THEIR REACTIVITY by LAKSHANI WATHSALA KULATHUNGAGE May 2025 Advisor: Dr. Stanislav Groysman Major: Chemistry (Inorganic) Degree: Doctor of Philosophy

This dissertation focuses on the synthesis and reactivity of transition metal and main group metal alkoxide complexes. The dissertation began with exploring a novel, efficient synthetic route towards transition metal alkoxides involving thallium reagents. A novel dimeric Tl2(OCtBu2Ph)2 complex was synthesized in the reaction between a lithium alkoxide and thallium precursor TlPF6. Tl2(OCtBu2Ph)2 served as a convenient precursor to the formation of old and new transition …

Structural Impacts Of Canonical And Non-Canonical Oligonucleotide Modifications, Deepak Shrestha

Wayne State University Dissertations

Nucleic acids, including DNA (deoxyribonucleic acid) and RNA (ribonucleic acids), are the fundamental building blocks of living organisms. The events that cause modification of DNA/RNA are of interest because they impact the nucleic acid function. Targeting DNA is important for treating diseases such as cancer. Cisplatin (cisPt) is a well-studied drug that targets DNA and blocks replication, but its use is limited by adverse side effects and cellular resistance. Prevoius research addressed some of these challenges through development of platinum analogues such as carboplatin and oxaliplatin. Amino acid-linked platinum analogues (AAPt) are the focus of this thesis work. AAPt complexes …

Direct Partial Oxidation Of Methane To Methanol Using Dioxygen Over Superhydrophobic Modified Catalysts, Oluchukwu V. Igboenyesi

Chemistry & Biochemistry Dissertations - Archive

Various methods for enhancing catalysts activity and productivity in gas to liquid synthesis like Direct Methane to Methanol Conversion and Fischer Tropsch Synthesis have been studied over the years. Some of these methods include the use of promoters, bifunctional catalysts, introducing steam, optimizing reaction conditions and catalyst modification. The choice of catalysts and their modification plays a critical role in improving the overall productivity in gas to liquid synthesis.

This research explored the superhydrophobic modification of heterogenous catalysts used in Direct Methane to Methanol Conversion (DMTM) and Fischer Tropsch Synthesis (FTS). The catalysts were modified with Perfluoro alkyls (PFSMA). The …

Copper-Based Oxide Semiconductors: Transparent Conductors And Ternary Alloys, Abhishek Rawat

Chemistry & Biochemistry Dissertations - Archive

This dissertation explores the strategic design and development of copper-based metal oxide semiconductors for photoelectrochemical (PEC) and optoelectronic applications, with a focus on advancing materials for sustainable energy technologies. Through a comprehensive investigation into copper vanadates and copper oxides, the work aims to understand and enhance charge transport, light-harvesting capabilities, and electronic structure modulation. The research integrates fundamental materials chemistry with applied photoelectrochemical studies to uncover the role of copper's d-electrons in mid-gap state formation, multifunctionality through electronic structure tuning, and the development of low-temperature transparent conductive oxides.

In chapter 2, we have discussed the attributes of copper metavanadate (CuV …

Raw Data For Tailoring High Entropy Borides For Hydrogenation: The Influence Of Crystal Morphology And The Exploration Of Catalytic Pathways, Michael Yeung, Ting Wang

Chemistry Department Faculty Scholarship

The high entropy boride (HEB) Al0.2Nb0.2Pt0.2Ta0.2Ti0.2B2, with its unique crystal structure and high coordination (platinum coordinated to 12 borons), has been shown in our previous work to exhibit exceptional catalytic properties, especially in sulfur-rich environments, where traditional platinum catalysts would succumb to sulfur-poisoning. In this work, we investigate the mechanism of the HEB catalyst, first by comparing the synthesis by flux growth, as previously reported, to an arc melted preparation. It is evident that the aluminum flux growth synthesis encourages the growth of single crystals, with clear and defined crystal facets, whereas the arc melted sample results in poorly defined …