Polymers for electronics and chemical sensing applications

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2006.Vita.Includes bibliographical references.The incorporation of molecular structures such as shape persistent molecular frameworks, strong hydrogen bond donor groups or perfluoro-alkyl groups can result in considerable gains in the performance of some established polymeric materials. This dissertation details the synthesis and properties of polymers that demonstrate such types of functionality for emerging electronics and chemical sensing applications. In Chapter 1, we present a general introduction to organic electronic materials and chemical sensory technologies. This chapter introduces many of the important principles that are explored throughout the rest of the text. In Chapters 2 and 3, we develop some novel polymeric materials for organic electronics applications. In Chapter 2, the development of several insulating polymers that demonstrate very high porosity in the solid state is discussed. The high porosity is provided by rigid three-dimensional frameworks, which present large amounts of internal free volume. In Chapter 3, we present the development of conducting polymeric materials that present rigid iptycene frameworks. These materials are prepared through an electro-chemical deposition process.(cont.) In Chapter 4, we find that the performance of an established conjugated polymer-based chemical sensory technology can be enhanced through the employment of pendant hexafluoroisopropanol groups that function as strong hydrogen bond-donating sorbant elements for weakly-binding analytes. In Chapter 5, we demonstrate that these hexafluoroisopropanol groups can be incorporated into a host of polymeric materials through a unique solid-state functionalization step that employs the reactive chemical hexafluoroacetone. These materials may be useful for analyte pre-concentration applications. Finally, in Chapter 6, we develop new, highly-luminescent conjugated polymers for future organic light-emitting diode-based display applications using hexafluoroacetone as a source of fluorination for the polymers. These materials demonstrate greater photo-oxidative stability that may extend their lifetimes in device applications.by John Paul Amara.Ph.D