In this study, our attention focuses upon the construction of metal-organic assemblies that direct the [2+2] photodimerization of olefins (e.g. trans-1,2-bis(4-pyridyl)ethylene) in the solid state. Such assemblies enable a means to combine the properties of metals with organic solid-state reactivity. Our synthetic strategy is based on the emergence of the fields of coordination and supramolecular chemistry and has lead to a series of photoactive metal-organic complexes. In particular, dinuclear Schiff-base Zn(II) complexes can be used to direct the arrangement of olefins in a way suitable for the [2+2] photodimerization reaction. We will demonstrate that the reactivity is maintained within derivatives of such templates, synthesized by attaching different functional groups to the peripheries and arms of the Schiff based ligands. We will also show that such solid-state reactivity can proceed via single-crystal-to-single-crystal reactions and lead to materials that exhibit highly controlled changes in fluorescence. A photoreactive assembly with a cavity that hosts molecules and anions as guests will also be described.