Halogen bonding to phosphorus atoms remains uncommon, with relatively few examples reported in the literature. In part 1 of the thesis, the preparation and investigation of the cocrystal (dicyclohexylphenylphosphine)(1,6-diiodoperfluorohexane) by X-ray crystallography and solid-state multinuclear magnetic resonance spectroscopy is described. The crystal structure features two crystallographically unique C-I···P halogen bonds (dI···P = 3.090(5) Å, 3.264(5) Å) and crystallographic disorder of one of the 1,6-diiodoperfluorohexane molecules. The first of these is the shortest and most linear I···P halogen bond reported to date. 13C, 19F, and 31P magic-angle spinning solid-state NMR spectra are reported. A 31P chemical shift change of -7.0 ppm in the cocrystal relative to pure dicyclohexylphenylphosphine, consistent with halogen bond formation, is noted. This work establishes iodoperfluoroalkanes as viable halogen bond donors when paired with phosphorus acceptors, and also shows that dicyclohexylphenylphosphine can act as a practical halogen bond acceptor. In part 2 of the thesis, computational work was done on nuclides of atoms which engage in the strongest halogen bonds (iodine, bromine, chlorine) that are all quadrupolar (spin I > ½). Previous group work reported extensive experimental NMR and NQR data relating 35/37Cl, 79/81Br, and 127I quadrupolar coupling information to local molecular structure in halogen bonded systems. Here, we make use of a new parameter, the valence p-orbital population anisotropy (VPPA), reported by Rinald and Wu, to increase our understanding of the origins of the electric field gradients (EFG) in halogen-bonded systems. Computations on model and real halogen-bonded cocrystalline systems using standard hybrid DFT methods are used to generate p-orbital populations and to compute the VPPA. We discuss the utility of the VPPA, and hence the EFG, as a tool to assess the ability of particular donors to engage in halogen bonds.