Flexibility in a Metal–Organic Framework Material Controlled by Weak Dispersion Forces: The Bistability of MIL‐53(Al)

Abstract

Breathtaking MOFs: DFT calculations reveal that the exceptional, thermally induced density change of the metal–organic framework MIL53(Al) is controlled by a competition between short- and long-range interactions and entropic factors. As shown in the picture (C green, Al cyan, O red, H white), dispersive interactions between the phenyl rings are responsible for stabilizing a narrow-pore form at low temperature. At 325–375 K, vibrational entropy causes the structure to expand markedly, permitting large volumes of light gases to be adsorbed.