TY - JOUR
T1 - Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal–Organic Framework
AU - Banerjee, Debasis
AU - Wang, Hao
AU - Plonka, Anna M.
AU - Emge, Thomas J.
AU - Parise, John B.
AU - Li, Jing
N1 - Funding Information:
The synthesis, gas adsorption and crystallographic work were performed at Rutgers University by D.B., H.W., T.J.E., and J.L. and were supported by US Department of Energy (DOE) through grant no. DE-FG02-08ER46491. The RU team would also like to acknowledge Micromeritics Instrument Corp. for an instrument award through its Instrument Grant program. The PXRD-DSC experiments by A.M.P. and J.B.P. at Stony Brook were supported by the US DOE, office of Basic Energy Sciences (BES) through grant no. BES DE-FG02-09ER46650.
PY - 2016
Y1 - 2016
N2 - Gate-opening is a unique and interesting phenomenon commonly observed in flexible porous frameworks, where the pore characteristics and/or crystal structures change in response to external stimuli such as adding or removing guest molecules. For gate-opening that is induced by gas adsorption, the pore-opening pressure often varies for different adsorbate molecules and, thus, can be applied to selectively separate a gas mixture. The detailed understanding of this phenomenon is of fundamental importance to the design of industrially applicable gas-selective sorbents, which remains under investigated due to the lack of direct structural evidence for such systems. We report a mechanistic study of gas-induced gate-opening process of a microporous metal–organic framework, [Mn(ina)2] (ina=isonicotinate) associated with commensurate adsorption, by a combination of several analytical techniques including single crystal X-ray diffraction, in situ powder X-ray diffraction coupled with differential scanning calorimetry (XRD-DSC), and gas adsorption–desorption methods. Our study reveals that the pronounced and reversible gate opening/closing phenomena observed in [Mn(ina)2] are coupled with a structural transition that involves rotation of the organic linker molecules as a result of interaction of the framework with adsorbed gas molecules including carbon dioxide and propane. The onset pressure to open the gate correlates with the extent of such interaction.
AB - Gate-opening is a unique and interesting phenomenon commonly observed in flexible porous frameworks, where the pore characteristics and/or crystal structures change in response to external stimuli such as adding or removing guest molecules. For gate-opening that is induced by gas adsorption, the pore-opening pressure often varies for different adsorbate molecules and, thus, can be applied to selectively separate a gas mixture. The detailed understanding of this phenomenon is of fundamental importance to the design of industrially applicable gas-selective sorbents, which remains under investigated due to the lack of direct structural evidence for such systems. We report a mechanistic study of gas-induced gate-opening process of a microporous metal–organic framework, [Mn(ina)2] (ina=isonicotinate) associated with commensurate adsorption, by a combination of several analytical techniques including single crystal X-ray diffraction, in situ powder X-ray diffraction coupled with differential scanning calorimetry (XRD-DSC), and gas adsorption–desorption methods. Our study reveals that the pronounced and reversible gate opening/closing phenomena observed in [Mn(ina)2] are coupled with a structural transition that involves rotation of the organic linker molecules as a result of interaction of the framework with adsorbed gas molecules including carbon dioxide and propane. The onset pressure to open the gate correlates with the extent of such interaction.
KW - coordination chemistry
KW - gas adsorption
KW - gate-opening
KW - hydrocarbon adsorption
KW - metal–organic frameworks
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U2 - 10.1002/chem.201601784
DO - 10.1002/chem.201601784
M3 - Article
AN - SCOPUS:84978296177
VL - 22
SP - 11816
EP - 11825
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 33
ER -