The analysis demonstrates the hierarchical nature of pore space for these crystalline materials with three unique pore sizes found within DUT-32, UMCM-1 and NU-1000. It was planned to also include DUT-75 for all aspects of this study, however, based on the pore size distribution only two peaks of pore sizes are observed. DUT-75 features three distinct pore environments and there are two pores, which although are different shapes and chemistry, almost identical in size. This prohibits an approach to dissect the pore environments based on size alone. No combination of limits could discern between these pores environments. The case of DUT-75 highlights the challenges that unique pore structures pose and necessitates an entirely different approach to extract the pores in this, and related, materials. The adsorption of Ar on DUT-32, UMCM-1 and NU-1000 was subsequently simulated using the established method of GCMC. The isotherms for each of the materials (Fig. ) demonstrate steps at different partial pressures corresponding to pore-filling events, common for mesoporous materials. NU-1000 features a gradual increase in amount adsorbed from 10E-5 to 10E-1 bar before rapidly increasing to saturation. This is very different to UMCM-1 and DUT-32 that both features sharp increases in amount adsorbed in two distinct steps. Generally, it is believed that the steps in isotherms of rigid materials are related to pore filling of different pore sizes.