New expanded porphyrins are of interest in terms of understanding the electrochemical features of oligopyrroles and the determinants of aromaticity. They can also act as ligands to stabilize metal complexes whose structures can differ from those of the better-studied porphyrins and, separately, have been explored for use in photodynamic and radiation therapy, among other application areas. With these considerations in mind, Chapter 1 is designed to provide a brief introduction to expanded porphyrin chemistry. Chapter 2 serves to detail our work on an expanded porphyrin called dipyriamethyrin. The emphasis will be on its preparation and the synthesis of the uranyl complex. Chapter 3 furthers this discussion with the synthesis of a related system, naphtho-isoamethyrin, as well as its bis-copper and uranyl complex. All work not carried out by the author will be specified as to give credit to those who provided the much appreciated help and guidance. Furthermore, the author hopes to present the science in such a manner wherein both the novice and expert can appreciate and understand the beauty of the underlying science