There is much interest in designing molecular sized containers that influence and facilitate chemical reactions within their nanocavities. On top of the advantages of improved yield and selectivity, the studies of reactions in confinement also give important clues that extend our basic understanding of chemical processes. We report here, the synthesis and self-assembly of an expanded bis-urea macrocycle to give crystals with columnar channels. Constructed from two C-shaped phenylethynylene units and two urea groups, the macrocycle affords a large pore with a diameter of similar to 9 angstrom. Despite its increased size, the macrocycles assemble into columns with high fidelity to afford porous crystals. The porosity and accessibility of these channels have been demonstrated by gas adsorption studies and by the uptake of coumarin to afford solid inclusion complexes. Upon UV-irradiation, these inclusion complexes facilitate the conversion of coumarin to its anti-head-to-head (HH) photodimer with high selectivity. This is contrary to what is observed upon the solid-state irradiation of coumarin, which affords photodimers with low selectivity and conversion.