Three dimensional molecular architectures for the synthesis and improved properties of high performance polymers

Abstract

Conjugated polymers have found various uses in optoelectronic applications, including chemical sensors, light-emitting diodes, and photovoltaic materials. In this thesis, we investigate the effect of having a molecular architecture that is both rigid and three-dimensional might play in the synthesis and performance of conjugated polymers. We discuss the efficient synthesis of a hydrophilic monomer bearing a threedimensional noncompliant array of hydroxyl groups that prevents water-driven excimer features of hydrophobic poly(p-phenylene ethynylene) backbones. We also use the detection of 3-nitrotyrosine as a probe to learn more about its physical state in solution. We further utilize the monomer above in a biocompatible post-polymerization functionalization reaction, taking advantage of the polymer's structural motif for the controllable attachment of biotin. The utility of this method is demonstrated for a model biosensor that responds to streptavidin. Finally, we discuss how rigid molecular architectures can be harnessed to bring two reacting groups together for the annulation of various [pi]-systems. The optical effects of the transformation are both notable and predictable, and the molecules have potential as monomers for conjugated polymer application in high performance organic light emitting diodes and photovoltaic devices.