Adsorption Contraction Mechanics: Understanding Breathing Energetics in Isoreticular Metal–Organic Frameworks

[Image: see text] A highly porous metal–organic framework DUT-48, isoreticular to DUT-49, is reported with a high surface area of 4560 m(2)·g(–1) and methane storage capacity up to 0.27 g·g(–1) (164 cm(3)·cm(–3)) at 6.5 MPa and 298 K. The flexibility of DUT-48 and DUT-49 under external and internal (adsorption-induced) pressure is analyzed and rationalized using a combination of advanced experimental and computational techniques. While both networks undergo a contraction by mechanical pressure, only DUT-49 shows adsorption-induced structural transitions and negative gas adsorption of n-butane and nitrogen. This adsorption behavior was analyzed by microcalorimetry measurements and molecular simulations to provide an explanation for the lack of adsorption-induced breathing in DUT-48. It was revealed that for DUT-48, a significantly lower adsorption enthalpy difference and a higher framework stiffness prevent adsorption-induced structural transitions and negative gas adsorption. The mechanical behavior of both DUT-48 and DUT-49 was further analyzed by mercury porosimetry experiments and molecular simulations. Both materials exhibit large volume changes under hydrostatic compression, demonstrating noteworthy potential as shock absorbers with unprecedented high work energies.