Synthesis, characterization and structural properties of fluorinated metal phthalocyanine chemiresistors for environmental parts-per-billion detection of toxic gases

Abstract

The doctoral thesis presented herein starts with an outline of the rich chemistry of MPc semiconducting platforms, presented in Chapter 1. The synthesis of numerous phthalocyanine semiconducting platforms is described in great detail on Chapter 2. Section 1 describes the synthesis of complexes with square planar geometry, more specifically, unsubstituted and hexadecafluorinated. Approaches in solution and solid state are compared and ultimately enhanced to generate polycrystalline powder materials with high degree of purity. On Section 2, we expand the coordination geometry of these systems to include axial-coordinated octahedral complexes. The synthesis of several unreported complexes will be described. The synthesis of phthalonitrile building blocks for the preparation of next generation substituted MPc systems is described on Sections 3 and 4 of Chapter 2, and further discussed in the upcoming Chapters. After successfully achieving the synthesis of high-purity semiconducting platforms, we characterized them readily through spectroscopic, microscopy, and crystallographic methods. An in-depth crystallographic analysis of the polycrystalline powders and nanowires is performed in Chapter 3, in addition to the gas sensing capabilities of the as-described complexes. Chapter 4 addresses the most critical points that were achieved during this thesis project, while Chapter 5 offers a future perspective of the endeavors that can be pursued with the knowledge generated in this thesis. All collaborative efforts are described in Appendix A, while Appendix B contains supplementary characterization data and Appendix C contains the crystallographic tables with respective bond lengths and angles of the published compounds.