Calculations were performed on transition-metal complexes to (1) extrapolate the structure and bonding of the ground and phosphorescent states (2) determine the luminescence energies and (3) assist in difficult assignment of luminescent transitions. In the [Pt(SCN)4]2- complex, calculations determined that the major excited-state distortion is derived from a b2g bending mode rather than from the a1g symmetric stretching mode previously reported in the literature. Tuning of excimer formation was explained in the [Au(SCN)2]22- by interactions with the counterion. Weak bonding interactions and luminescent transitions were explained by calculation of Hg dimers, excimers and exciplexes formed with noble gases.
Three different types of cage crown ethers have been prepared and their complexation properties with Ag(I) have been studied. Atomic absorption, fluorescence quenching, and UV absorption have been used to study the interaction between the hosts (cage crown ethers) and guests (Ag+). For the cage-annulated crown ethers that contain aromatic rings, cation-π and π-π interactions may contribute significantly to the overall complexation ability of the host system. Piperazine groups may cooperate, and the piperazine nitrogen atoms provide unshared electrons, which may form a complex with Ag+. In addition, relatively soft donor atoms (e.g., Br) are well-suited for complexation with Ag+, which is a softer Lewis acid than alkali metal cations.
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.
Organometallic catalysis has attracted significant interest from both industry and academia due to its wide applications in organic synthetic transformations. Example of such transformations include the reaction of a zinc carbenoid with olefins to form cyclopropanes. The first project is a computational study using both density functional and correlated wavefunction methods of the reaction between ethylene and model zinc carbenoid, nitrenoid and oxenoid complexes (L-Zn-E-X, E = CH2, NH or O, L = X = I or Cl). It was shown that cyclopropanation of ethylene with IZnCH2I and aziridination of ethylene with IZnNHI proceed via a single-step mechanism with an asynchronous transition state. The reaction barrier for the aziridination with IZnNHI is lower than that of cyclopropanation. Changing the leaving group of IZnNHI from I to Cl, changes the mechanism of the aziridination reaction to a two-step pathway. The calculation results from the epoxidation with IZnOI and ClZnOCl oxenoids suggest a two-step mechanism for both oxenoids. Another important example of organometallic catalysis is the formation of alkyl arenes from arenes and olefins using transition metal catalysis (olefin hydroarylation). We studied with DFT methods the mechanism of a novel Rh catalyst (FlDAB)Rh(TFA)(η2–C2H4) [FlDAB = N,N’ -bis(pentafluorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene; TFA = trifluoroacetate] that converts benzene, ethylene and air-recyclable Cu(II) oxidants to styrene. Possible mechanisms are discussed.
A computational chemistry analysis combined with a crystallographic database study of the bonding in late transition metal N-heterocyclic carbene (NHC) complexes is reported. The results illustrate a metal-carbon bond for these complexes, approximately 4% shorter than that of a M-C single bond found in metal alkyl complexes. As a consequence of this result, two hypotheses are investigated. The first hypothesis explores the possibility of multiple-bond character in the metal-carbon linkage of the NHC complex, and the second, considers the change in the hybridization of the carbenoid carbon to incorporate more p character. The latter hypothesis is supported by the results. Analysis of these complexes using the natural bond orbital method evinces NHC ligands possessing trans influence.
The square-planar tetracyanonickelate(II) anion was intercalated into 2:1 and 3:1 Mg-Al layered double hydroxide systems (LDHs). In the 2:1 material, the anion holds itself at an angle of about 30° to the layers, whereas in the 3:1 material it lies more or less parallel to the layers. This is confirmed by orientation effects in the infrared spectra of the intercalated materials and by X-ray diffraction (XRD) data. The measured basal spacings for the intercalated LDH hosts are approximately 11 Å for the 2:1 and approximately 8 Å for the 3:1. The IR of the 2:1 material shows a slight splitting in the ν(CN) peak, which is suppressed in that compound's oriented IR spectrum, indicating that at least some of the intercalated anion's polarization is along the z-axis. This effect is not seen in the 3:1 material. A comparison between chloride LDHs and nitrate LDHs was made with respect to intercalation of tetracyanonickelate(II) anions. Both XRD data and atomic absorption spectroscopy (AAS) data of the LDH tetracyanonickelates confirms that there are no significant differences between the products from the two types of starting materials. The presence of a weak ν(NO) peak in the IR spectra of those samples made from nitrate parents indicates the presence of small amounts of residual [NO3]- in those systems. Small amounts of Cl- present in the chloride-derived samples, while perhaps detectable using AAS, would not be detectable in this manner. An attempted synthesis of Mg-Al LDH carbonates starting from reduced Mg and Al was unsuccessful due to pH constraints on hydroxide solubility in the solvent system used (water). The pH required to precipitate Al(OH)3 in the system was too high to allow precipitation of Mg(OH)2. Consequently, we found it impossible to have both of the required metal hydroxides present simultaneously in the system. An additional synthesis …
Various gold complexes were computationally investigated, to probe their photophysical, geometric, and bonding properties. The geometry of AuI complexes (ground state singlet) is very sensitive to the electronic nature of the ligands: σ-donors gave a two-coordinate, linear shape; however, σ-acceptors yielded a three-coordinate, trigonal planar geometry. Doublet AuIIL3 complexes distort to T-shape, and are thus ground state models of the corresponding triplet AuIL3. The disproportionation of AuIIL3 to AuIL3 and AuIIIL3 is endothermic for all ligands investigated, however, σ-donors are better experimental targets for AuII complexes. For dimeric AuI complexes, only one gold center in the optimized triplet exciton displays a Jahn-Teller distortion, and the Au---Au distance is reduced versus the ground state distance (i.e., two reasons for large Stokes' shifts).
Glutathione syntethase (GS) is an enzyme that belongs to the ATP-grasp superfamily and catalyzes the second step in the biosynthesis of glutathione. GS has been purified and sequenced from a variety of biological sources; still, its exact mechanism is not fully understood. Four highly conserved residues were identified in the binding site of human GS. Additionally, the G-loop residues that close the active site during catalysis were found to be conserved. Since these residues are important for catalysis, their function was studied computationally by site-directed mutagenesis. Starting from the reported crystal structure of human GS, different conformations for the wild type and mutants were obtained using molecular dynamics technique. The key interactions between residues and ligands were detected and found to be essential for enzyme activity.
A 13C and 6Li variable temperature NMR study of 2-ethylbutyllithium/lithium 2-ethyl-1-butoxide mixed aggregates formed from reacting 2-ethyl-1-butanol with 2-ethylbutyllithium in two O/Li ratios of 0.2/1 and 0.8/1. The 0.2/1 sample resulted in two 2-ethylbutyllithium/lithium 2-ethyl-1-butoxide mixed aggregates and seven lithium hydride/lithium 2-ethyl-1-butoxide mixed aggregates. The lithium hydride mixed aggregates were also studied using selective 1H decoupling experiments. The 0.8/1 sample resulted in six 2-ethylbutyllithium/lithium 2-ethyl-1-butoxide mixed aggregates and five lithium hydride/lithium 2-ethyl-1-butoxide mixed aggregates. A low temperature 13C NMR spectroscopy study of n-pentyllithium indicated three aggregates, most likely a hexamer, an octamer, and a nonamer. A low temperature 13C NMR study of an 0.2/1 O/Li ratio sample of n-pentyllithium mixed with 1-pentanol resulted in three n-pentyllithium/lithium n-pentoxide aggregates mixed aggregates along with the three n-pentyllithium aggregates. 13C NMR data for this mixture gave inconclusive results whether or not lithium hydride/lithium alkoxide mixed aggregates were present in the sample.
An NMR spectroscopy study of trimethylsilylmethyllilthium, TMSM-Li, indicates that TMSM-Li exists as two different aggregates in cyclopentane solution. Using previously reported colligative properties of TMSM-Li in different solutions in connection with new 13C and 6Li NMR data collected in this study, aggregation states were assigned as octamer and hexamer. Low temperature 13C and 6Li NMR peak intensities indicated an equilibrium exists between the two aggregates that shifts toward the octamer as the temperature decreases. ΔH was calculated to be 5.23 + 0.15 kcal/mol and ΔS was calculated to be 17.9 + 0.6 eu for the hexamer/octamer equilibrium system. Samples of TMSM-Li were mixed with TMSM-OH in attempts to form mixed alkyllithium/lithium alkoxide aggregates. 13C NMR data for these mixtures gave inconclusive results whether or not these compounds formed, which is different from other primary alkyllithium compounds studied in the past. A study of neopentyllithium, NpLi, indicates only one aggregate in solution with the aggregation state unknown using low temperature 13C NMR spectroscopy.
The luminescence properties of Van Der Waals' dimers and clusters of pyrene and diazapyrene have been investigated. Excimers, dimeric species which are associative in an excited electronic state and dissociative in their ground state, have long been established and play an important role in many areas of photochemistry. My work here focuses on the luminescence and absorption properties of ground state dimers/aggregates, which are less understood, and allows further characterization of the ground state and excited state association of these aromatic molecules.
Treatment of 4,5 bis-(diphenylphosphino)-cyclopenten-1,3 dione with thiophene carboxyaldehyde in dichloromethane, in the presence of molecular sieves results in a new heterocyclic compound, 2-(2-thienylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (ligand), with a high yield. This product was characterized by using both IR and NMR spectroscopic techniques and the solid-state structure of the ligand was determined using X-ray crystallography. When the ligand was treated with the solvent stabilized intermediate of ReBr(CO)5 with THF, a monomeric metal complex, fac-BrRe(CO)3[2-(2-thienylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione] was the result. The solid-state structure of the monomeric metal complex was determined using X-ray crystallography. Photolysis and thermolysis studies of the complex will be further explored.
Chiral gold complexes have been applied in homogeneous catalytic reactions since 1986, in some cases with high enantioselectivity. Acyclic diaminocarbene (ADC) ligands are acyclic analogues of N-heterocyclic carbenes (NHCs) that have larger N-CCarbene-N angles and stronger donating ability. ADCs have been developed as alternatives to phosphine and NHC ligands in homogeneous gold catalysis. In 2012, a new series of chiral gold(I) ADCs were first developed by Slaughter's group and were shown to give remarkable enantioselectivities in some reactions. Because of the hindered rotation of the N-CCarbene bonds of ADC, chiral ADC substituents can easily get close to the metal center in some conformations, although two rotameric structures are formed if the chiral amine is nonsymmetric. The selective of specific ADC conformations was the initial focus of this study. Formational selectivity of one diastereomer of an ADC ligand during synthesis was examines by measuring the relative rates of diastereomer formation in a 1H NMR kinetic study. The potential for converting multiple conformational isomers of ADCs into a single conformation, or at least a simpler mixture, was examined. This study used the analogy that anti- isomer has electronic and structural similarity with urea/thiourea, raising the possibility that 1,8-naphthyridine can be used to favor certain conformations through a self-assembled hydrogen-bonding complex. Gold(I) is a soft carbophilic Lewis acid able to active C-C π bonds to nucleophilic attack, and ADC-gold complexes are potentially useful in this regard. Therefore, biaryl gold(I) ADC complexes were examine with silver salt additives in catalytic 1,6-enyne cyclization reaction. A detailed study found that the counteranion affects the regioselectivities of these reactions more than substituents on the ancillary ADC ligands.
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