A pair of framework-catenation isomers (UPC-19 and UPC-20) based on an anthracene-functionality dicarboxylate ligand were synthesized and characterized for the first time through tuning of the dimensionality of interpenetration. The interpenetration dimensionality significantly influences the properties including the porosity, gas-uptake capacity, and fluorescent sensing ability: UPC-19 with 5-fold interpenetration is nonporous, whereas the 3-fold interpenetration form of UPC-20 is porous and exhibits selective adsorption of CO2 and fluorescent sensing of Cu2+ and Fe3+ through fluorescence quenching.