The long-distance charge transfer process in ferrocene-based MOFs with FeO6 clusters boosts photocatalytic CO2 chemical fixation.

Metal nodes and organic ligands are important structural units of MOFs, and their properties can profoundly affect the photocatalytic activity. Herein, two ferrocene-based MOFs with FeO 6 or AlO 6 clusters as the metal nodes and 1,1′-ferrocenedicarboxylic acid (H 2 FcDC) as the ligands were successfully synthesized. Comparing with normal organic ligands, ferrocene ligands have longer-lived photogenerated charges due to metal-to-ligand charge transfer (MLCT) process, leading to a better photocatalytic activity of the corresponding ferrocene-based MOFs. In addition, the FeO 6 clusters are able to further accept the photogenerated electrons from ferrocene ligands compared to the inert AlO 6 clusters, allowing a long-distance charge transfer process, namely the proposed metal-to-ligand-to-metal charge transfer (MLMCT) process, which results in a better performance towards photocatalytic CO 2 cycloaddition reaction. This work sheds a light on designing MOFs using ferrocene ligands with high photocatalytic activity. [Display omitted] • The MLCT process possessed by H 2 FcDC was proved to be beneficial to prolong the lifetime of photogenerated charge carriers over ferrocene-based MOFs. • FeO 6 clusters in Fe-FcDC can accept the photogenerated electrons from ferrocene ligands and a novel MLMCT process was proposed. • Fe-FcDC exhibits an outstanding activity towards photo-driven CO 2 cycloaddition under mild conditions with a yield of 283.8 mmol/(g h). [ABSTRACT FROM AUTHOR]

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