Mechanical Gating of Redox Access in Molecular Electrocatalysis

Molecular electrocatalysis is commonly interpreted through electronic descriptors, implicitly treating catalysts as mechanically passive during redox cycling. Yet, electron transfer often imposes structural demands on molecular scaffolds, raising the question of whether internal mechanical constraints can directly regulate access to reactive states and, in turn, catalytic outcomes. Addressing this question has remained challenging because mechanical effects are typically inseparable from changes in composition or electronic structure. Here, we achieve this separation by exploiting two constitutionally identical molecular catalysts whose only distinction is ligand geometry. This minimal geometric variation enables or suppresses intramolecular hydrogen bonding, thereby encoding distinct mechanical constraints that isolate molecular mechanics as a variable in redox accessibility. In the α isomer, molecular constraints impose a mechanically enforced barrier that severely limits access to the reactive redox state. This disrupts the temporal ordering of elementary steps, and diverts reactivity toward competing hydrogen evolution, eroding both selectivity and stability. In contrast, mechanical compliance in the β isomer enables facile access to the redox-active state, allowing CO₂ activation to intrinsically outpace water activation and yielding CO selectivities exceeding 92%. Operando spectroscopy and real-time mass spectrometry, combined with computational simulation, directly resolve this mechanically gated reaction sequence as it unfolds. Molecular mechanics thus emerge as determinants that link electron flow to reaction sequencing and catalytic selectivity, revealing that constitutionally similar catalysts can be mechanically, and therefore catalytically, distinct.