Four structurally diverse coordination polymers1-4(CP1-CP4) were designed and constructed from Cd(ii) ions and various carboxyl ligands (H2oba, 4,4′-oxydibenzoic acid; H2bpa, (E)-4,4′-(ethene-1,2-diyl)dibenzoic acid; H2pbda, 4,4′-((1,3-phenylenebis(methylene))bis(oxy))dibenzoic acid) and the alkene containing ligand (CH3-bpeb, 4,4′-((1E,1′E)-(2,5-dimethyl-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine).CP1-CP4possess Cd2binuclear secondary building units (SBUs). The geometry of the dicarboxylate ligands and the reaction conditions determined the final structure with a variety of motifs.CP1possesses an interdigitated 2D structure, whileCP2consists of a 1D channel-like motif with isolated CH3-bpeb molecules embedded in the channels. The solid-state structure ofCP3consists of two unique layers interpenetrated to form a 2D + 2D → 2D polycatenated backbone, while a 1D channel-like motif filled by isolated CH3-bpeb molecules was observed forCP4. In all four coordination polymers pairs of CH3-bpeb molecules were bound or encapsulated by the Cd2secondary building units at an appropriate distance and orientation for solid-state [2 + 2] photodimerization of one pair of C=C bonds. Desolvation ofCP3with heat resulted in a decrease in solid-state fluorescence and a slowing of the rate of solid-state photodimerization.