We present a unified thermodynamic description of the breathing transitions between large pore (lp) and narrow pore (np) phases of MIL-53 (Cr) observed during the adsorption of guest molecules and the mechanical compression in the process of mercury porosimetry. By revisiting recent experimental data on mercury intrusion and in situ XRD during CO(2) adsorption, we demonstrate that the magnitude of the adsorption stress exerted inside the pores by guest molecules, which is required for inducing the breathing transition, corresponds to the magnitude of the external pressure applied from the outside that causes the respective transformation between lp and np phases. We show that, when a stimulus is applied to breathing MOFs of MIL-53 type, these materials exhibit small reversible elastic deformations of lp and np phases of the order of 2-4%, while the breathing transition is associated with irreversible plastic deformation that leads to up to ∼40% change of the sample volume and a pronounced hysteresis. These results shed light on the specifics of the structural transformations in MIL-53 (Cr) and other soft porous crystals (SPC).

We present a multiscale physical mechanism and a stochastic model of breathing transitions, which represent adsorption-induced structural transformations between large pore and narrow pore conformations in bistable metal-organic frameworks, such as MIL-53. We show that due to interplay between host framework elasticity and guest molecule adsorption, these transformations on the level of crystal occur via layer-by-layer shear. We construct a simple Hamiltonian that describes the physics of host-host and host-guest interactions and show that a respective Monte Carlo simulation model qualitatively reproduces the experimentally observed features of breathing transitions. np layer lp layers lp layers shearing MIL-53 breathing: layer-by-layer mechanism