Direct structural evidence of commensurate-to-incommensurate transition of hydrocarbon adsorption in a microporous metal organic framework† †Electronic supplementary information (ESI) available: Experimental procedures gas-adsorption data and crystallographic data. CCDC 1051641, 1051643–1051647 and 1427863. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc03685b ‡These authors contributed equally to this work

Structural evidence of commensurate-to-incommensurate transition of linear hydrocarbon molecules in a MOF. The efficiency of physisorption-based separation of gas-mixtures depends on the selectivity of adsorbent which is directly linked to size, shape, polarizability and other physical properties of adsorbed molecules. Commensurate adsorption is an interesting and important adsorption phenomenon, where the adsorbed amount, location, and orientation of an adsorbate are commensurate with the crystal symmetry of the adsorbent. Understanding this phenomenon is important and beneficial as it can provide vital information about adsorbate–adsorbent interaction and adsorption–desorption mechanism. So far, only sporadic examples of commensurate adsorption have been reported in porous materials such as zeolites and metal organic frameworks (MOFs). In this work we show for the first time direct structural evidence of commensurate-to-incommensurate transition of linear hydrocarbon molecules (C 2 –C 7 ) in a microporous MOF, by employing a number of analytical techniques including single crystal X-ray diffraction (SCXRD), in situ powder X-ray diffraction coupled with differential scanning calorimetry (PXRD-DSC), gas adsorption and molecular simulations.