Redox enzyme-inspired design of metalloporphyrin-based catalysts

Redox enzymes are excellent catalysts for many chemical reactions due to their high selectivity and efficiency. The direct use of natural redox enzymes in chemical synthesis presents multiple challenges, including instability, high cost, and limited availability. Designing artificial catalysts that can closely mimic the core function of redox enzymes to suit diverse chemical reactions is a feasible strategy to mitigate these challenges. Here, we provide an overview of the molecular design of catalysts containing a metalloporphyrin motif and their applications in chemical and electrochemical synthesis. We particularly emphasize the development of organic auxiliary groups as ligands and distal functionalities that coordinate to the metal center of the metalloporphyrin and render a push and a pull effect, respectively. The progress in designing enzyme-inspired catalysts to enable tuning of catalytic activity and pathways for various chemical and electrochemical reactions is comprehensively discussed. The discussion also extends to material designs involving axial ligands and/or distal groups. Finally, we present the challenges and opportunities for enzyme-inspired catalysts in sustainable energy and chemical production. • Axial and distal groups play an integral role in enhancing the catalytic ability of heme-based redox enzymes. • The push effect of axial ligands reduces activation energy, increases reaction rates, and/or alters reaction pathways. • The pull effect of distal groups destabilizes the bonds within a reaction intermediate, thereby lowering the bond cleavage energy. • The auxiliary design mimics the natural redox enzyme, enhancing catalytic performance. • Advanced material chemistries allow for the creation of metalloporphyrin-based catalysts for practical chemical and electrochemical reactions.