Inspired by the significance and utility of hydrogen bond driven self-assembly, as exemplified through base-pairing interactions of double helical DNA, this dissertation discusses the synthetic preparation and structural analysis of a number of functionalized supramolecular ensembles derived from nucleic acid base-pairing. Specifically, three projects are detailed. Each of these projects, although under the general purview of basepairing, addresses a distinct issue in the field of molecular recognition. The first chapter will serve to introduce the general modalities of base-pairing as well as provide an overview of the diverse synthetic supramolecular ensembles that have been prepared by exploiting such interactions. Chapter 2 will detail the development and self-assembly properties of a novel guanosine-cytidine dinucleoside, which is capable of forming a cyclic ensemble through Watson-Crick hydrogen bonding. Chapter 3 will focus on the development of a porphyrin-fullerene derived photoinduced electron transfer model system, which self-assembles via Watson-Crick base-pairing interactions. Chapter 4 will introduce a new pyrrole-tethered purine nucleoside, which is capable of forming an extended three-point Hoogsteen-type base-pairing interaction with guanosine. In addition, this chapter will also investigate the capability of this purine derivative in disrupting guanosine-derived self-association. At the end of each of these chapters, a section pertaining to ongoing efforts and proposed future research is included. Chapter 5 provides experimental methods and characterization data.