Expanding the Structural Topologies of Rare-Earth Porphyrinic Metal–Organic Frameworks through Ligand Modulation

Expanding the structural diversity of porphyrinic metal–organic frameworks (PMOFs) is essential to develop functional materials with novel properties or enhanced performance in different applications. Herein, we establish a strategy to construct rare-earth (RE) PMOFs with unprecedented topology via rational functionalization of porphyrinic ligands. By introducing phenyl/pyridyl groups to the meso-positions of the porphyrin core, the symmetries and connectivities of the ligands are tuned, and three RE-PMOFs (BUT-224/-225/-226) with new topologies are successfully obtained. In addition, BUT-225(Co), with both the Lewis basic and acidic sites, exhibits enhanced CO₂ uptake and higher catalytic activity for the cycloaddition of CO₂ and epoxides under mild conditions. This work reveals that the RE-PMOFs with novel topologies can be rationally designed and constructed through ligand functionalization, which provides insights into the construction of tailored PMOFs for various applications.