Development of Supramolecular Framework Catalyst Constructed by the Self‐Assembly of Iron‐Porphyrin Complexes Bearing Ar‐Ar F Interaction Sites for Photochemical CO 2 Reduction

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The reduction of carbon dioxide (CO 2 ) into value‐added compounds is a promising strategy for addressing environmental and energy challenges. Molecule‐based heterogeneous catalysts are attractive because they combine the structural tunability of molecule‐based catalysts with the durability and recyclability of heterogeneous systems. Herein, we report the construction of a supramolecular framework catalyst via the self‐assembly of iron‐porphyrin complexes bearing arene‐perfluoroarene (Ar‐Ar F ) interaction sites. Single‐crystal x‐ray structural analysis revealed that the porphyrin complexes form one‐dimensional (1D) columnar structures via intermolecular interactions between the interaction sites, which further organize into a porous crystalline framework stabilized by multiple noncovalent interactions. The resulting supramolecular framework ( [Fe‐TPEP] cryst ) functions as a molecule‐based heterogeneous catalyst for photochemical CO 2 reduction, exhibiting high selectivity for carbon monoxide (CO) formation. Comparative studies using a nonporous material bearing iron‐porphyrin‐based catalytic centers demonstrate that [Fe‐TPEP] cryst shows enhanced catalytic activity, indicating the importance of the porous structure for the efficient catalysis.