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<p> When chloropentafluoroacetone in the gas phase at room temperature is electronically excited in the ultraviolet region, emission is observed. This emission is assigned to a transition from the 1 (n,π*) state. Deactivation of the vibrationally excited singlet state can occur when the ketone is excited at short wavelengths. The internal heavy atom effect on both radiative and radiationless transitions from the excited singlet state is relatively small. The quenching of the chloroketone molecules in the zeroth vibrational level of the excited singlet state has been studied and the probable quenching mechanisms proposed. Intersystem crossing from the excited singlet state to the triplet state is an important process in the gas phase at room temperature. However, phosphorescence is observed only in matrices at low temperatures, e.g. 77°K. The internal heavy atom effect on radiative and radiationless transitions from the triplet state in the matrix at low temperature is small. </p> / Thesis / Doctor of Philosophy (PhD)

<p> The products and mechanism of the photolytic rearrangement of the equilibrium mixture of triphenylmethylcyclopentadienes have been studied. Direct irradiation of the equilibrium mixture of triphenylmethylcyclopentadienes yields 5,6,6-triphenylbicyclo{3.1.0}hex-2-ene. Photolysis with a triplet sensitizer yields dimeric products in addition to 5,6,6-triphenylbicyclo{3.1.0}hex-2-ene. Thermolytic isomerization of 5,6,6-triphenylbicyclo{3.1.0}hex-2-ene is reported. The predominant isomer in the equilibrium mixture of triphenylmethylcyclopentadiene has been established as 2-triphenylmethylcyclopentadiene.</p> / Thesis / Master of Science (MSc)

The importance of addressing environmental issues such as lowering the emission of greenhouse gases, preventing eutrophication of aquatic life due to high concetrations of nitrogen oxyanions, and producing sustainable energy is at an all-time high. With a concentration on employing earth abundant metals, a Mn(I) complex was synthesized with an integrated photocatalyst in an attempt at developing a new electrophotocatalytic system. Additionally, a Ni(II) pincer complex was synthesized and structurally and computationally characterized as well as observed to perform electrocatalytic hydrogen generation in water. Lastly, with inspiration from the Ni(II) pincer complex, two macrocyclic complexes, one with a Ni(II) center and the other with a Co(II) center, were structurally characterized and observed to electrocatalytically reduce aqueous nitrite at neutral pH. DFT calculations were also performed to elucidate the nitrite reduction reaction mechanism.

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