10.1021/ja312115x.s001 Manuel Tsotsalas Manuel Tsotsalas Pavel Hejcik Pavel Hejcik Kenji Sumida Kenji Sumida Ziya Kalay Ziya Kalay Shuhei Furukawa Shuhei Furukawa Susumu Kitagawa Susumu Kitagawa Impact of Molecular Clustering inside Nanopores on Desorption Processes American Chemical Society 2013 Molecular Clustering PCP vapor molecules Desorption ProcessesUnderstanding impact desorption rate gas purge nanoporous systems chemical nature interaction metastable state sorption kinetics desorption process proceeding guest molecules 2013-03-27 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Impact_of_Molecular_Clustering_inside_Nanopores_on_Desorption_Processes/2430634 Understanding the sorption kinetics of nanoporous systems is crucial for the development and design of novel porous materials for practical applications. Here, using a porous coordination polymer/quartz crystal microbalance (PCP/QCM) hybrid device, we investigate the desorption of various vapor molecules featuring different degrees of intermolecular (hydrogen bonding) or molecule-framework interactions. Our findings reveal that strong intermolecular interactions lead to the desorption process proceeding via an unprecedented metastable state, wherein the guest molecules are clustered within the pores, causing the desorption rate to be temporarily slowed. The results demonstrate the considerable impact of the chemical nature of an adsorbate on the kinetics of desorption, which is also expected to influence the efficiency of certain processes, such as desorption by gas purge.