Solvent‐Induced Control over Breathing Behavior in Flexible Metal–Organic Frameworks for Natural‐Gas Delivery

Finding appropriate stimuli for controlling the breathing behavior of flexible metal-organic frameworks (MOFs) is highly challenging. Herein, we report the solvent-induced changes in the particle size and stability of different breathing phases of the MIL-53 series, a group of flexible MOFs. A water/dimethylformamide (DMF) ratio is tuned to synthesize members of the MIL-53 series which have different behaviors. The breathing is explored by high-pressure methane sorption tests. Increasing DMF concentration decreases MOF particle size and increases the stability of the porous phases, boosting the 5.8-65 bar sorption difference of methane, which is required for natural-gas delivery.