The purpose of this tutorial review is to address the use of metal ions to mediate reactions in the organic solid state. We describe metal complexes and coordination networks that facilitate dimerizations, oligomerizations and polymerizations of olefins and acetylenes via irradiation (e.g. ultraviolet (UV) and (60)Co gamma-rays) and thermal annealing. We show how metal ions can be utilized to direct the formation of polymers and molecules. We also describe how supramolecular chemistry has recently influenced dimerization processes in self-assembled metal-organic solids.