The fascinating role that porphyrins play in natural processes such as photosynthesis and respiration, continues to provide a compelling motivation to study these chromophores and to design new analogues with improved functions. This dissertation describes the interdisciplinary study of several classes of compounds that include π-extended porphyrins, expanded porphyrins, porphycenes, polypyrroles and porphyrins. Dictated by the need to capture efficiently red and near-infrared light, the so-called π-extension approach has been established as a powerful tool in the synthesis of large aromatic chromophores. Many of these artificial systems demonstrate properties similar to natural porphyrins. Often, however, a reduced bandgap is seen due to a greater π-system. Synthetic challenges associated with the preparation of the linearly annulated porphyrins have long been recognized. Many of these have now beed overcome as the result of a newly developed synthetic protocol described in Chapter 1. This protocol allows for the synthesis of a pyrrolic building block under milder conditions. As a continuation of this work, naphthobipyrroles were obtained via the π-extension strategy applied to a benzobipyrrole. The utility of this new building block was demonstrated with the syntheses of an electrochromic polynaphthobipyrrolic polymer (Chapter 3) and a dinaphthoporphycene (Chapter 2), a chromophore isomeric to porphyrin. Chapter 4 describes a different approach to porphyrin functionalization. Here, the goal was to effect substitution at the so-called β pyrrolic positions with using two bithiophene groups. Although, the resulting product is not completely rigid, enhancement in the sensitizing properties of the basic porphyrin chromophore was seen in a dye sensitized solar cell (DSSC) assembly, as studied by scanning electrochemical microscopy (SECM). The synthetic contributions concerning this work, carried in collaboration with Bard group, are expected to lay the groundwork for the development future photovoltaic materials. Expanded porphyrins are the more diverse group of porphyrinic derivatives. In effort to develop new conjugated expanded porphyrin systems and to understand their spectroscopic behavior in greater detail, a set of expanded porphyrins, based on the direct electrochemical oxidation of terpyrrole-like fragments, was developed in conjunction with the Bucher group (Grenoble, France). This effort is described in Chapter 5. Specifically it is shown that trithiacyclo[9]pyrrole may be prepared by means of an electrochemical synthesis. / text