Out-of-Equilibrium Confinement Catalysis Mediated by Compressive Force

Abstract

Biological systems utilize continuous energy inputs, such as light or chemical fuels, to sustain non-equilibrium states essential for life. In contrast, synthetic systems typically dissipate energy toward equilibrium, revealing a fundamental thermodynamic disparity compared to biological systems. Here, we demonstrate that mechanical force, delivered via ball-milling, serves as a unique energy source to drive endergonic coordination self-assembly inaccessible through conventional stimuli. Mechanistic studies, such as ball-milling reaction kinetics, model reactions, and DFT calculations, revealed that coordination cages under direct mechanical impact are highly deformed, elevating their ground-state energies. These distorted cages enable barrier-free guest release followed by cage reassembly. By coupling this force-driven step with a subsequent equilibrium process, two unprecedented outcomes were achieved: (1) an out-of-equilibrium catalytic confinement cycle and (2) a dissipative cycle. Notably, this mechanochemical strategy circumvents product inhibition, a persistent challenge in equilibrium-based supramolecular systems, enabling transformations with up to 85 catalytic turnovers, previously unattainable due to inhibitory guest binding. Our work underscores the untapped potential of mechanical force as a powerful tool to design non-equilibrium chemical processes and dynamic, life-like systems.