Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 11816-11825 |
| Number of pages | 10 |
| Journal | Chemistry - A European Journal |
| Volume | 22 |
| Issue number | 33 |
| DOIs | |
| Publication status | Published - 2016 |
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Keywords
- coordination chemistry
- gas adsorption
- gate-opening
- hydrocarbon adsorption
- metal–organic frameworks
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal–Organic Framework. / Banerjee, Debasis; Wang, Hao; Plonka, Anna M.; Emge, Thomas J.; Parise, John B.; Li, Jing.
In: Chemistry - A European Journal, Vol. 22, No. 33, 2016, p. 11816-11825.Research output: Contribution to journal › Article
}
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
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
UR - http://www.scopus.com/inward/record.url?scp=84978296177&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84978296177&partnerID=8YFLogxK
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 -