Switchable molecular electrocatalysis.

We demonstrate a switchable electrocatalysis mechanism modulated by hydrogen bonding interactions in ligand geometries. By manipulating these geometries, specific electrochemical processes at a single catalytic site can be selectively and precisely activated or deactivated. The α geometry enhances dioxygen electroreduction (ORR) while inhibiting protium redox processes, with the opposite effect seen in the β geometry. Intramolecular hydrogen bonding in the α geometry boosts electron density at the catalytic center, facilitating a shift of ORR to a 4-electron pathway. Conversely, the β geometry promotes a 2-electron ORR and facilitates electrocatalytic hydrogen evolution through an extensive proton charge assembly; offering a paradigm shift to conventional electrocatalytic principles. The expectations that ligand geometry induced electron density modulations in the catalytic metal centre would have a comparable impact on both ORR and HER has been questioned due to the contrasting reactivity exhibited by α-geometry and β-geometry molecules. This further emphasizes the complex and intriguing nature of the roles played by ligands in molecular electrocatalysis.