Inorganic Chemistry Commons^™

Synthesis Of Novel Alkaline Earth Metal Acetylides, Eva Baker

Honors Capstone Projects - All

Acetylide complexes of the heavy alkaline-earth metals were first introduced by our group. With our group being interested in how the ligand and donor affect the structural chemistry of the resulting complexes, my project was focused on the detailed analysis of past work and the extension towards new ligand and donor sets. The work required the analysis and development of synthetic procedures towards these highly reactive species.

Past synthetic work in our group had established several synthetic routes towards the target compounds including transamination and toluene elimination. Using toluene elimination, I was able to reproduce the synthesis of M(C≡CSiPh_{3 …}

U.S.-Russia Cooperative Research: Designing Gold(I) Complexes For New Materials, Alice E. Bruce, Mitchell Bruce, Dmitri Lemenosvsii, Victor Dyadchenko,

University of Maine Office of Research Administration: Grant Reports

This award in International Programs and the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports collaborative research by Dr. Alice E. Bruce of the University of Maine and Dr. Dmitri Lemenovskii of Moscow State University (Russia). The goal of the project is to design gold complexes that will be useful in new materials, such as liquid crystals. Organogold compounds containing rod-shaped molecules will be synthesized and structurally characterized. Lattice effects in liquid and solid phases formed from the compounds will be studied. Both groups are experienced in the synthetic aspects of the research, but will take advantage of the University of …

The Thermochemistry Of 2,4-Pentanedione Revisited: Observance Of A Nonzero Enthalpy Of Mixing Between Tautomers And Its Effects On Enthalpies Of Formation, Manuel Temprado, Maria Victoria Roux, Patamaporn Umnahanant, Hui Zhao, James S. Chickos

James Chickos

No abstract provided.

Bi(Iii) Initiated Cyclization Reactions And Iodonium Fragmentation Kinetics, Yajing Lian

Dissertations, Theses, and Masters Projects

No abstract provided.

Ultra-Fast Formation Of Stable Nanoparticle Film Assemblies, Dan Sheibley, Renee Szymanik, Michael C. Leopold

Chemistry Faculty Publications

Novel assembled films of monolayer-protected clusters (MPCs) can be grown on gold and glass substrates with a 20-fold higher efficiency than established procedures. Thick MPC films grown using this new method, which can easily be scaled up or automated, are extremely stable and have properties identical to traditionally formed nanoparticle films, including unique quantized double layer charging effects. This new procedure for growing nanoparticle films shares the versatility of the traditional method but exhibits accelerated growth attributed to highly efficient sorption and mobility of metal ion linkers within swelled films and improved mass transfer of nanoparticles to assembly sites. Concentration …

Nondipole Effects In The Photoionization Of Xe 4d5/2 And 4d3/2: Evidence For Quadrupole Satellites, Oliver Hemmers, Renaud Guillemin, D. Rolles, A. Wolska, Dennis W. Lindle, K. T. Cheng, W. R. Johnson, H. L. Zhou, S. T. Manson

Environmental Studies Faculty Publications

Measurements of nondipole parameters in spin-orbit-resolved Xe 4d photoionization demonstrate dynamical differences arising from relativistic effects. The experimental data do not agree with relativistic random-phase approximation calculations of single ionization dipole and quadrupole channels. It is suggested that the discrepancy is due to the omission of multiple-excitation quadrupole channels, i.e., quadrupole satellite transitions.

Nearest-Neighbor-Atom Core-Hole Transfer In Isolated Molecules, Renaud Guillemin, Oliver Hemmers, D. Rolles, S. W. Yu, A. Wolska, I. Tran, A. C. Hudson, J. Baker, Dennis W. Lindle

Environmental Studies Faculty Publications

A new phenomenon sensitive only to next-door-neighbor atoms in isolated molecules is demonstrated using angle-resolved photoemission of site-selective core electrons. Evidence for this interatomic core-to-core electron interaction is observable only by measuring nondipolar angular distributions of photoelectrons. In essence, the phenomenon acts as a very fine atomic-scale sensor of nearest-neighbor elemental identity.

Self-Assembly Of Inorganic Membranes: Attachment Of Gold Nanoparticles To A Mesoporous Silica Membrane, Jennifer K. Saucier

Honors College

The purpose of this study was to investigate the self-assembly of gold nanoparticles to create thin, densely packed structures several monolayers thick for the synthesis of a membrane. Silica membrane synthesis was examined as a support for deposition of the nanoparticles. Pore size formation and thickness were controlled to promote high flux, defect free layer formation while providing for optimum separation. Silica mesoporous membranes were created through the acid-catalyzed hydrolysis of tetraethyl orthosilicate. An ionic block co-polymer was used to control a networked pore formation. The silica sols were dip coated on macroporous alumina supports. The silica membranes were characterized …

Triethylammonium Tetraphenylborate Dichloromethane Solvate, Daron E. Janzen, Kent R. Mann

Daron E Janzen, Ph.D.

No abstract provided.

Distance-Dependent Electron Hopping Conductivity And Nanoscale Lithography Of Chemically-Linked Gold Monolayer Protected Cluster Films, Francis P. Zamborini, Laura E. Smart, Michael C. Leopold, Royce W. Murray

Chemistry Faculty Publications

Films of monolayer protected Au clusters (MPCs) with mixed alkanethiolate and ω-carboxylate alkanethiolate monolayers, linked together by carboxylate–Cu2+–carboxylate bridges, exhibit average edge-to-edge cluster spacings that vary with the numbers of methylene segments in the alkanethiolate ligand as determined by a combined atomic force microscopy (AFM)/UV-Vis spectroscopy method. The electronic conductivity (σEL) of dry films is exponentially dependent on the cluster spacing, consistent with electron tunneling through the alkanethiolate chains and non-bonded contacts between those chains on individual, adjacent MPCs. The calculated electronic coupling factor (β) for tunneling between MPCs is 1.2 Å−1, which is similar to …

Growth, Conductivity, And Vapor Response Properties Of Metal Ion-Carboxylate Linked Nanoparticle Films, Michael C. Leopold, Robert L. Donkers, Dimitra Georganopoulou, Megan Fisher, Francis P. Zamborini, Royce W. Murray

Chemistry Faculty Publications

Nanoparticles of metals (Au, Ag, Pd, alloys) in the size range 1–3 nm diameter can be stabilized against aggregation of the metal particles by coating the metal surface with a dense monolayer of ligands (thiolates). The stabilization makes it possible to analytically define the nanoparticle composition (for example, Au140(hexanethiolate)53, I) and to elaborate the chemical functionality of the protecting monolayer (for example, Au140(C6)35(MUA)18, II, where C6 = hexanethiolate and MUA = mercaptoundecanoic acid). Network polymer films (IIfilm) on interdigitated array electrodes can be prepared from II, based on cation coordination (i.e., Cu2+, Zn2+, Ag+, methyl viologen) by the …

Dramatic Nondipole Effects In Low-Energy Photoionization: Experimental And Theoretical Study Of Xe 5s, Oliver Hemmers, Renaud Guillemin, E. P. Kanter, B. Krassig, Dennis W. Lindle, S. H. Southworth, R. Wehlitz, J. Baker, A. C. Hudson, M. Lotrakul, D. Rolles, Wayne C. Stolte, I. Tran, A. Wolska, S. Yu, M. Ya Amusia, K. T. Cheng, L. V. Chernysheva, W. R. Johnson, S. T. Manson

Environmental Studies Faculty Publications

The Xe 5s nondipole photoelectron parameter γ is obtained experimentally and theoretically from threshold to ∼200  eV photon energy. Significant nondipole effects are seen even in the threshold region of this valence shell photoionization. In addition, contrary to previous understanding, clear evidence of interchannel coupling among quadrupole photoionization channels is found.

E1-E2 Interference In The Vuv Photoionization Of He, E. P. Kanter, B. Krassig, S. H. Southworth, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, R. Wehlitz, M. Ya Amusia, L. V. Chernysheva, N. L. S. Martin

Environmental Studies Faculty Publications

We have measured the forward-backward asymmetry of photoelectron angular distributions produced in the vacuum ultraviolet photoionization of helium. This asymmetry, a consequence of the breakdown of the dipole approximation, measures the real part of the ratio of the quadrupole and dipole matrix elements. In the autoionization region, the strong energy dependence of the asymmetry permits an experimental separation of the ratio of those magnitudes from their phase difference. We experimentally determined the Fano parameters of the 2p²¹D₂ quadrupole resonance, and report improved values of the width Γ and line profile parameter q from those previously available …

Reactions Of Alcohols And Organophosphonates On Tungsten Trioxide Epitaxial Films, Shuguo Ma

Electronic Theses and Dissertations

The adsorption, diffusion, reactions, and desorption of water, alcohols, ethers, and an organophosphonate were studied using calibrated thermal desorption spectroscopy (CTDS) on thin film WO₃(OOl) surfaces grown epitaxially on a single crystal α- Al₂O₃(li02) (sapphire) substrate. The studies were conducted on oxidized and reduced surfaces, which were characterized by x-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). The desorption spectra for molecular desorption of all of these molecules shifted to lower temperature with increasing coverage, and had overlapping tails on the high temperature side. Monte Carlo simulations show that this typical desorption shape …

Surface Interactions Of Mercury On Gold Foil Electrodes In Electrodeposition And Stripping And ; An Investigation Of Free Thiolate Ions From Metal-Thiolate Chalcogenides, Charles Martin Watson

Electronic Theses and Dissertations

Mercury, a highly toxic metal, whose environmental concentration magnifies with ascension of the food chain, is monitored in our waters, food and air. Monitoring mercury is generally done by sample collection, transport to the laboratory; followed by: digestion of the sample, separation of the mercury and detection of the mercury: mostly by cold vapor atomic absorption or, cold vapor atomic fluorescence. These monitoring methods, preclude, routine, in-the-field mercury determination. New analytical techniques have been proposed for in the field determination of mercury. They consist of mercury adsorption onto a sensor or electrode and measuring how much is there either as …

Raman Spectroscopy Of Rhombohedral P4o10, Sean J. Gilliam, Scott Kirkby, Clifton N. Merrow, Daniel Zeroka, Ajit Banerjee, James O. Jensen

Scott J. Kirkby

Heat Capacities Of Thiane Sulfones And Thiane Sulfoxide: Refining Of Cp Group Values For Organosulfur Compounds And Their Oxides, Marı́A Victoria Roux, Manuel Temprado, Pilar Jiménez, Ramón Guzmán-Mejı́A, Eusebio Juaristi, James S. Chickos

James Chickos

No abstract provided.

Argon Eximer Emission From High-Pressure Microdischarges In Mental Capillaries, R. Mohan Sankaran, Konstantinos P. Giapis, Mohamed Moselhy, Karl H. Schoenbach

Bioelectrics Publications

We report on argon excimer emission from high-pressure microdischarges formed inside metal capillaries with or without gas flow. Excimer emission intensity from a single tube increases linearly with gas pressure between 400 and 1000 Torr. Higher discharge current also results in initial intensity gains until gas heating causes saturation or intensity drop. Argon flow through the discharge intensifies emission perhaps by gas cooling. Emission intensity was found to be additive in prealigned dual microdischarges, suggesting that an array of microdischarges could produce a high-intensity excimer source.

Stabilization Of Polyvinyl Chloride By Some Conducting Polymers, Amit Shah, Brian C. Berry, Ali U. Shaikh

Journal of the Arkansas Academy of Science

No abstract provided.

Silica Supported Copper Complexes And Their Biomimetic Activities, Jun Wang

Dissertations, Theses, and Masters Projects

No abstract provided.

Reactions Of Boranes And Metallaboranes With Phosphines, Lawrence Barton, Oleg Volkov, Mitsuhiro Hata, Paul Mcquade, Nigam Rath

Chemistry & Biochemistry Faculty Works

This paper reports extensions of the well-established field of phosphine–borane chemistry. Linked clusters, for example, {[(PPh3)2(CO)OsB4H7-3-BH2-PPh2]2 [(Fe(C5H4)2]}, are formed in reactions of rigid backboned bidentate phosphines with {2,2,2-(PPh3)2(CO)-nido-2-OsB5H9]. Reaction of bidentate phosphines with the unsaturated clusters [8,8-PPh3)2-nido-8,7-RhSB9H10] and [9,9-(PPh3)2-nido-9,7,8-RhC2B8 H11] leads to the isolation of novel species such as {1-(PPh3)[1,3-(µ-dppm)]-closo -1,2-RhSB9H8},with a dppm molecule bridging adjacent metal and boron vertices in the cage, [1,1-(ç2-dppe)-3-(ç1-dppm)-closo-1,2-RhSB 9H8], a mixed ligand system, and {9,9-ç2-[(ç2-BH3)PPh2PCH2 PPh2]-nido- 9,7,8-RhC2B8H11} which contains a bidentate dppm BH3 moiety. The formation of bidentate phosphine-linked main group transition-metal moieties such as [BH3PPh2(CH)nPPh2IrCp*Cl2] is also described as is an example of …

Chlorobenzenes And Chloronitrobenzenes Interaction With Iron (O), Manuel Alejandro Serratos

Masters Theses

Degradation of chlorobenzene, dichlorobenzenes and chloronitrobenzenes (ClB, x-Cl2B and x-ClNO2B) was tested by trying to make them react with metallic iron, Fe (0), in water solvent.

The experiments consisted of optimizing the parameters of the reactions (like minimum mass of iron needed) and analytical detection conditions. Analytical techniques used were gas and liquid chromatography (GC and HPLC), mass spectrometry (MS) and UV-Vis spectroscopy.

No substances other than the initial ClB and x-Cl2B were detected in their tests with Fe (0) after shaking for periods of up to three days, although 10%weight average decreases in concentration were observed.

The ClNO2B isomers …

Reactions Of Boranes And Metallaboranes With Phosphines, Lawrence Barton, Oleg Volkov, Mitsuhiro Hata, Paul Mcquade, Nigam P. Rath

Nigam Rath

Simulation Of Structure, Dynamics And Electron Diffraction Patterns Of Heterogeneous Clusters Armn2N, W. H. Jinasena

Electronic Theses and Dissertations

The nitrogen-argon system provides a useful paradigm for studying segregation and mixing behavior in heterogeneous clusters. Using three realistic pair potentials corresponding to argon-argon, nitrogen-nitrogen and argon-nitrogen interactions, the structures and thermodynamics of Ar_m(N₂)_n, clusters are investigated. Comparison of these results to previous simulation results on neat argon and nitrogen clusters is made. The initial focus of the study is the series of thirteen particle clusters of Ar_m(N₂)_13-m (0 ≤ m ≤ 13); molecular dynamics in the microcanonical ensemble is the principle simulation tool. The icosahedral nitrogen-argon clusters …

Stabilization Of Rutile-Related Thin Film On Tio2 Substrates, Youngnam Cho

Electronic Theses and Dissertations

Conducting metal oxide thin films are of broad interest because they have a wide variety of magnetic and electronic properties. Materials exist that range from superconducting to insulating, are ferromagnetic and are ferroelectric. These properties make thin conducting oxide films attractive for many industrial applications. A class of metal oxides exists that adapt the rutile crystal structure; the structure of the mineral rutile, TiO₂. These metal oxides have the general formula MO₂ where M is a metal cation of valence +4. Metal oxides crystallizing in the rutile structure also display a wide variety of physical properties. The …

The Enthalpy Of Vaporization And Sublimation Of Corannulene, Coronene, And Perylene At T = 298.15 K, James S. Chickos, Paul Webb, Gary Nichols, Tetsu Kiyobayashi, Pei-Chao Cheng, Lawrence Scott

James Chickos

No abstract provided.

Non-Dipolar Electron Angular Distributions From Fixed-In-Space Molecules, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, E. Shigemasa, K. Le Guen, D. Ceolin, C. Miron, N. Leclercq, P. Morin, Marc Simon, P. W. Langhoff

Environmental Studies Faculty Publications

The first indication of nondipole effects in the azimuthal dependence of photoelectron angular distributions emitted from fixed-in-space molecules is demonstrated in N₂. Comparison of the results with angular distributions observed for randomly oriented molecules and theoretical derivations for the nondipole correction first order in photon momentum suggests that higher orders will be needed to describe distributions measured in the molecular frame.

Electron Hopping Conductivity And Vapor Sensing Properties Of Flexible Network Polymer Films Of Metal Nanoparticles, Francis P. Zamborini, Michael C. Leopold, Jocelyn F. Hicks, Pawel J. Kulesza, Marcin A. Malik, Royce W. Murray

Chemistry Faculty Publications

Films of monolayer protected Au clusters (MPCs) with mixed alkanethiolate and ω-carboxylate alkanethiolate monolayers, linked together in a network polymer by carboxylate-Cu2+-carboxylate bridges, exhibit electronic conductivities (σEL) that vary with both the numbers of methylene segments in the ligands and the bathing medium (N2, liquid or vapor). A chainlength-dependent swelling/contraction of the film's internal structure is shown to account for changes in σEL. The linker chains appear to have sufficient flexibility to collapse and fold with varied degrees of film swelling or dryness. Conductivity is most influenced (exponentially dependent) by the chainlength of the nonlinker (alkanethiolate) ligands, a result consistent …

Photoexcitation Of A Dipole-Forbidden Resonance In Helium, B. Krassig, E. P. Kanter, S. H. Southworth, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, R. Wehlitz, N. L. S. Martin

Environmental Studies Faculty Publications

We have observed photoexcitation of the dipole-forbidden 1s²¹S₀→2p²¹D₂ resonance in helium by measuring the nondipolar forward-backward asymmetry of photoelectron angular distributions in the 2ℓ2ℓ^′ autoionizing region. By exploiting the electric dipole-quadrupole interference in the excitation of both the 2s2p¹P₁ and 2p²¹D₂ levels, we have observed the quadrupole resonance in photoabsorption and extracted its Fano line shape parameters and the relative phase of the 1sEp and 1sEd continua. We find the quadrupole line profile index q₂ to be markedly different from theoretical expectations.

An On-Line Acid-Base Titration Applet In The Generic Tutorial System For The Sciences Project, Thomas Lee Gummo

Theses Digitization Project

The purpose of this Master's Project was to develop an Acid-Base Titration Simulator. It was also to be a part of the California State University - San Bernardino's GTSS, Generic Tutorial System for the Sciences, project. The main benefit is that students will be able to conduct titration experiments over the Internet without being in the laboratory and without costly equipment or dangerous chemicals. Instructors at the high school and college level can demonstrate the key principles of titration.