Abstract Pore‐shape fixing effects (PSFEs) in soft porous crystals are a relatively unexplored area of materials chemistry. We report the PSFE in the prototypical dynamic van der Waals solid p‐tert‐butylcalix4arene (TBC4). Starting with the high‐density guest‐free phase, two porous shape‐fixed phases were programmed using the stimuli of CO2 pressure and temperature. A suite of complementary in situ techniques, including variable‐pressure (VP) single‐crystal X‐ray diffraction, VP powder X‐ray diffraction, VP differential scanning calorimetry, volumetric sorption analysis, and attenuated total reflectance Fourier‐transform infrared spectroscopy was used to track dynamic guest‐induced transformations, providing molecular‐level insight into the PSFE. The interconversion between the two metastable phases is particle size dependent, making this the second example of the PSFE by crystal downsizing, and the first example involving a porous molecular crystal: larger particles undergo reversible transitions while smaller particles remain fixed in the metastable phase. A complete phase interconversion scheme was constructed for the material, thus allowing navigation of the phase interconversion landscape of TBC4 using the easily applied stimuli of CO2 pressure and thermal treatment.
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