New examples of chlorophosphinochlorophosphonium (4) and chlorophosphinodichlorophosphonium (5) cations have been prepared and spectroscopically characterized. These bifunctional phosphinophosphonium cations offer a new approach to the development of phosphinophosphonium frameworks using reductive coupling reactions and have been exploited as synthons to assemble larger catena-phosphorus cations. The reactions of 4 and 5 with stibine reducing agents have been studied using P-31 NMR spectroscopy and have been shown to produce a variety of new and known frameworks in a facile manner, depending on the reducing agent selection and the stoichiometry of the reaction. New derivatives of frameworks containing three, four, and five phosphorus atoms have been identified by P-31 NMR spectroscopy. Crystals of the [GaCl4](-) salt of the five-membered dication 11(Pr-i) have been isolated from the reaction of [4(Pr-i)][GaCl4] with SbBu3, and the solid state structural features and solution state dynamics are comprehensively described in the context of P-31{H-1} NMR spectroscopic observations.