Publications

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Our team has investigated a series of soluble coordination complexes for use as tags to monitor underground fluid flows in reservoirs. While most of the metal-ligand (M-L) complexes were based on the dianionic salen family of ligands, conceptually other ligands such as porphyrins or phthalocyanines could be used with similar success. Detection and identification of these species in solution were performed by inductively coupled plasma (ICP) or Raman/resonance Raman (rR) spectroscopy. The preparation of a large number of new M-L salen complexes was accomplished. Complexes were prepared that were soluble in either water or hydrocarbons to allow for flexibility in use. Unambiguous identification of these complexes allowed for meaningful molecular dynamics (MD) calculations to be performed, so that the attraction of the M-L complexes to either the rock formation or the liquid media could be evaluated. The use of soluble M-L species was found to avoid issues of rock deposition.

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The P,P-chelated heteroleptic complex bis[bis(diisopropylphosphino)amido]indium chloride [(i-Pr2P)2N]2InCl was prepared in high yield by treating InCl3 with 2 equiv of (i-Pr2P)2NLi in Et2O/tetrahydrofuran solution. Samples of [(i-Pr2P)2N]2InCl in a pentane slurry, a CH2Cl2 solution, or in the solid state were exposed to CO2, resulting in the insertion of CO2 into two of the four M-P bonds to produce [O2CP(i-Pr2)NP(i-Pr2)]2InCl in each case. Compounds were characterized by multinuclear NMR and IR spectroscopy, as well as single-crystal X-ray diffraction. ReactIR solution studies show that the reaction is complete in less than 1 min at room temperature in solution and in less than 2 h in the solid-gas reaction. The CO2 complex is stable up to at least 60°C under vacuum, but the starting material is regenerated with concomitant loss of carbon dioxide upon heating above 75°C. The compound [(i-Pr2P)2N]2InCl also reacts with CS2 to give a complicated mixture of products, one of which was identified as the CS2 cleavage product [Si=P(i-Pr2)NP(i-Pr2)]2InCl]2(μ-Cl)[μ-(i-Pr2P)2N)].

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Reaction of [κ²-PR₂C(SiMe₃)Py]₂Zn (R = Ph, 2a; ⁱPr, 2b) with CO₂ affords the products of formal insertion at the C–Si bond, [κ²-PR₂CC(O)O(SiMe₃)Py]₂Zn (R = Ph, 3a; ⁱPr, 3b). Insertion product 3b was structurally characterized. As a result, the reaction appears to be a stepwise insertion and rearrangement of CO₂ based on kinetic data.

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This late-start LDRD was focused on the application of chemical principles of self-assembly on the ordering and placement of photovoltaic cells in a module. The drive for this chemical-based self-assembly stems from the escalating prices in the 'pick-and-place' technology currently used in the MEMS industries as the size of chips decreases. The chemical self-assembly principles are well-known on a molecular scale in other material science systems but to date had not been applied to the assembly of cells in a photovoltaic array or module. We explored several types of chemical-based self-assembly techniques, including gold-thiol interactions, liquid polymer binding, and hydrophobic-hydrophilic interactions designed to array both Si and GaAs PV chips onto a substrate. Additional research was focused on the modification of PV cells in an effort to gain control over the facial directionality of the cells in a solvent-based environment. Despite being a small footprint research project worked on for only a short time, the technical results and scientific accomplishments were significant and could prove to be enabling technology in the disruptive advancement of the microelectronic photovoltaics industry.

Energy production is inextricably linked to national security and poses the danger of altering the environment in potentially catastrophic ways. There is no greater problem than sustainable energy production. Our purpose was to attack this problem by examining processes, technology, and science needed for recycling CO{sub 2} back into transportation fuels. This approach can be thought of as 'bio-inspired' as nature employs the same basic inputs, CO{sub 2}/energy/water, to produce biomass. We addressed two key deficiencies apparent in current efforts. First, a detailed process analysis comparing the potential for chemical and conventional engineering methods to provide a route for the conversion of CO{sub 2} and water to fuel has been completed. No apparent 'showstoppers' are apparent in the synthetic route. Opportunities to improve current processes have also been identified and examined. Second, we have also specifically addressed the fundamental science of the direct production of methanol from CO{sub 2} using H{sub 2} as a reductant.