Tuning the High‐Pressure Phase Behaviour of Highly Compressible Zeolitic Imidazolate Frameworks: From Discontinuous to Continuous Pore Closure by Linker Substitution

The high‐pressure behaviour of flexible zeolitic imidazolate frameworks (ZIFs) of the ZIF‐62 family with the chemical composition M(im)(2−x )(bim)(x) is presented (M(2+)=Zn(2+), Co(2+); im(−)=imidazolate; bim(−)=benzimidazolate, 0.02≤x≤0.37). High‐pressure powder X‐ray diffraction shows that the materials contract reversibly from an open pore ( op ) to a closed pore ( cp ) phase under a hydrostatic pressure of up to 4000 bar. Sequentially increasing the bim(−) fraction (x) reinforces the framework, leading to an increased threshold pressure for the op ‐to‐ cp phase transition, while the total volume contraction across the transition decreases. Most importantly, the typical discontinuous op ‐to‐ cp transition (first order) changes to an unusual continuous transition (second order) for x≥0.35. This allows finetuning of the void volume and the pore size of the material continuously by adjusting the pressure, thus opening new possibilities for MOFs in pressure‐switchable devices, membranes, and actuators.