Guest adsorption in the nanoporous metal–organic framework Cu3(1,3,5-benzenetricarboxylate)2: combined in situ x-ray diffraction and vapor sorption

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dc.contributor.authorPeterson, VKen_AU
dc.contributor.authorSouthon, PDen_AU
dc.contributor.authorHalder, GJen_AU
dc.contributor.authorPrice, DJen_AU
dc.contributor.authorBevitt, JJen_AU
dc.contributor.authorKepert, CJen_AU
dc.date.accessioned2016-10-18T00:34:19Zen_AU
dc.date.available2016-10-18T00:34:19Zen_AU
dc.date.issued2014-07-23en_AU
dc.date.statistics2016-10-18en_AU
dc.description.abstractThe structure of the nanoporous metal–organic framework Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylate) with a variety of molecular guests was studied in situ using single crystal X-ray diffraction. By collecting crystal structure data for a series of guests within the same host crystal, insights into the molecular interactions underpinning guest adsorption processes have been gained. Adsorption behaviors are influenced strongly by both enthalpic and entropic thermodynamic, as well as interpore steric (size-exclusion) effects, and we note correlations between guest attributes and these effects. Vapor adsorption measurements revealed a guest uptake capacity inversely proportional to guest size. Correspondingly, structural results show that guests reside in the smallest pores accessible to them. Interpore steric effects for larger guests cause these to be excluded from the smallest pores, and this corresponds to lower total uptake. Both hydrophilic and lipophilic small guests adsorb favorably into the 5 Å diameter smallest pore of the material, with the number of guests in these pores dependent on guest size and their location, in turn dependent upon both guest–guest interactions and competition between hydrogen-bonding interactions at the apertures of the smallest pore and lipophilic interactions at the center of the smallest pore. Hydrophilic guests with lone electron pairs interact preferentially with the coordinatively unsaturated Cu sites of the desolvated framework, with the number of these depending on steric interactions between neighboring bound guests and guest flexibility. Guest coordination at the Cu sites has a significant effect on the framework structure, increasing the Cu···Cu distance in the dinuclear unit, with the Cu3(BTC)2 unit cell being smaller when guests that do not coordinate with the Cu are present, and in the case of cyclohexane, smaller than for the desolvated framework. Overall, our comprehensive structural study reconciles Cu3(BTC)2 adsorption properties with the underlying guest–host and guest–guest interactions that gives rise to these. © 2014, American Chemical Society.en_AU
dc.identifier.citationPeterson, V. K., Southon, P. D., Halder, G. J., Price, D. J., Bevitt, J. J., & Kepert, C. J. (2014). Guest adsorption in the nanoporous metal–organic framework Cu3(1,3,5-benzenetricarboxylate)2: combined in situ x-ray diffraction and vapor sorption. Chemistry of Materials, 26(16), 4712-4723. doi:10.1021/cm501138gen_AU
dc.identifier.govdoc7340en_AU
dc.identifier.issn0897-4756en_AU
dc.identifier.issue16en_AU
dc.identifier.journaltitleChemistry of Materialsen_AU
dc.identifier.pagination4712-4723en_AU
dc.identifier.urihttp://dx.doi.org/10.1021/cm501138gen_AU
dc.identifier.urihttp://apo.ansto.gov.au/dspace/handle/10238/7778en_AU
dc.identifier.volume26en_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectX-ray diffractionen_AU
dc.subjectEntropyen_AU
dc.subjectThermodynamic activityen_AU
dc.subjectMetalsen_AU
dc.subjectHydrogenen_AU
dc.subjectCyclohexaneen_AU
dc.titleGuest adsorption in the nanoporous metal–organic framework Cu3(1,3,5-benzenetricarboxylate)2: combined in situ x-ray diffraction and vapor sorptionen_AU
dc.typeJournal Articleen_AU
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