Abstract
Biological systems sustain non-equilibrium states through continuous energy inputs such as light or chemical fuels, whereas synthetic systems typically dissipate energy toward equilibrium. 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 combining ball-milling kinetics, model reactions, and density functional theory (DFT) calculations reveal that direct mechanical impact strongly deforms coordination cages, 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 are achieved: (1) an out-of-equilibrium catalytic confinement cycle and (2) a dissipative cycle. Notably, this mechanochemical strategy circumvents product inhibition in equilibrium-based supramolecular systems, enabling transformations with up to 85 catalytic turnovers. Our work highlights mechanical force as a design principle for non-equilibrium chemistry toward life-like systems.
Fangzi Liu
Visiting PhD Student
