Supramolecular chemistry aims to exploit non-covalent interactions and subsequently engineer molecules that self-assembly into specific 3D arrangements. In the solid-state, UV-light can be used to achieve reactivity, through [2+2] photocycloadditions, when reactant molecules meet specific criteria. My dissertation focuses on using complementary molecules that act as templates to arrange molecules close in proximity. This solvent-free method has allowed the synthesis of an aldehyde-functionalized cyclobutane and generation of new molecules capable of unique, complex 3D arrangements.