MOFs Under Pressure: The Reversible Compression of a Single Crystal

Abstract

The structural change and resilience of a single crystal of a metal–organic framework (MOF), Zn­(HO₃PC₄H₈PO₃H)·2H₂O (ZAG-4), was investigated under high pressures (0–9.9 GPa) using <i>in situ</i> single crystal X-ray diffraction. Although the unit cell volume decreases over 27%, the quality of the single crystal is retained and the unit cell parameters revert to their original values after pressure has been removed. This framework is considerably compressible with a bulk modulus calculated at ∼11.7 GPa. The <i>b</i>-axis also exhibits both positive and negative linear compressibility. Within the applied pressures investigated, there was no discernible failure or amorphization point for this compound. The alkyl chains in the structure provide a spring-like cushion to stabilize the compression of the system allowing for large distortions in the metal coordination environment, without destruction of the material. This intriguing observation only adds to the current speculation as to whether or not MOFs may find a role as a new class of piezofunctional solid-state materials for application as highly sensitive pressure sensors, shock absorbing materials, pressure switches, or smart body armor