Synthesis and characterization of phosphorus-containing inorganic polymers

This research project involves the synthesis of novel phosphorus-containing inorganic polymers. These materials share similar structures to their organic counterparts but are not comprised entirely of hydrocarbons as the latter. As such they may serve as replacements for organic materials, a growing concern as the price of petroleum feed stocks continues to increase. Paper 1 investigates transesterification polymerizations of poly(alkylene phosphonates) through phosphorous and proton nuclear magnetic resonance spectroscopy. A methyl-transfer side reaction was identified and steps to eliminate it's occurrence were created. This also allowed for the elimination of a dangerous step in the synthesis procedure. Paper 2 investigates the functionalization of bithiophene with diphenylphosphino substituents and the subsequent reaction of these ligands with molybdenum tetracarbonyl systems. This led to the formation of a cyclic oligomer and prompted the synthesis of the edge and corner models also described therein. Paper 3 investigated the nonlinear optical properties of diphenylphosphino-substituted terthiophenes and their palladium and platinum chloride complexes. Thianaphthenes were also investigated in this paper but had no appreciable activity. The terthiophene materials displayed the first reported observation of third-order nonlinear behavior in these types of systems. Paper 4 reports the crystal structure of bis-2-diphenylphosphinoterthiophene palladium chloride in a previously unknown morphology. Through unintentional variation of crystallization conditions a new crystal structure of this compound was achieved.