High-Pressure in Situ ¹²⁹Xe NMR Spectroscopy and Computer Simulations of Breathing Transitions in the Metal–Organic Framework Ni₂(2,6-ndc)₂(dabco) (DUT-8(Ni))

Recently, we have described the metal–organic framework Ni2(2,6-ndc)2(dabco), denoted as DUT-8(Ni) (DUT = Dresden University of Technology, 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane). Upon adsorption of molecules such as nitrogen and xenon, this material exhibits a pronounced gate-pressure effect which is accompanied by a large change of the specific volume. Here, we describe the use of high-pressure in situ 129Xe NMR spectroscopy, i.e., the NMR spectroscopic measurements of xenon adsorption/desorption isotherms and isobars, to characterize this effect. It appears that the pore system of DUT-8(Ni) takes up xenon until a liquid-like state is reached. Deeper insight into the interactions between the host DUT-8(Ni) and the guest atom xenon is gained from ab initio molecular dynamics (MD) simulations. van der Waals interactions are included for the first time in these calculations on a metal–organic framework compound. MD simulations allow the identification of preferred adsorption sites for xenon as well as insight into the breathing effect at a molecular scale. Grand canonical Monte Carlo (GCMC) simulations have been performed in order to simulate adsorption isotherms. Furthermore, the favorable influence of a sample pretreatment using solvent exchange and drying with supercritical CO2 as well as the influence of repeated pore opening/closure processes, i.e., the “aging behavior” of the compound, can be visualized by 129Xe NMR spectroscopy.