Synthesis and Metalation of Expanded Porphyrins and their Building Blocks
Porphyrin and related tetrapyrrolic macrocycles, collectively porphyrinoids, are versatile ligands that allow access to a multitude of coordination modes. Judicious modification of the porphyrin core, as well as the pendant substituents, have extended the coordination chemistry of porphyrinoids to include systems that are able to stabilize f-block element complexes with concomitant access to new structures with possible utility. Here our group’s efforts to prepare porphyrinoid ligands and their building blocks, that can serve as tools to study and apply f-element metal coordination chemistry are described, including the background of the topic, selected syntheses, and application of these species in the chemical and medical sciences. My thesis research spans three projects, including the synthesis and characterization of an amethyrin-uranyl complex displaying aromatic character, the iterative synthesis of tuneable α,α’-linked oligoheterocycles displaying fluorescent properties, and the gram-scale synthesis of a bench-stable 5,5”-unsubsituted terpyrrole.