Examining the Effects of Different Ring Configurations and Equatorial Fluorine Atom Positions on CO 2 Sorption in [Cu(bpy) 2 SiF 6 ]

Handle URI:
http://hdl.handle.net/10754/598267
Title:
Examining the Effects of Different Ring Configurations and Equatorial Fluorine Atom Positions on CO 2 Sorption in [Cu(bpy) 2 SiF 6 ]
Authors:
Forrest, Katherine A.; Pham, Tony; Nugent, Patrick; Burd, Stephen D.; Mullen, Ashley; Wojtas, Lukasz; Zaworotko, Michael J.; Space, Brian
Abstract:
Simulations of CO2 sorption were performed in a metal-organic material (MOM) that is part of a "SIFSIX" family of compounds that has remarkable carbon dioxide capture and separation properties. The MOM considered here has the formula [Cu(bpy)2SiF6] (bpy = 4,4′-bipyridine). This hydrophobic MOM is both water-stable and CO 2-specific with significant sorption capacity under ambient conditions. The crystal structure reveals bpy rings and equatorial fluorine atoms in multiple possible orientations; the static disorder has been modeled based on single-crystal X-ray diffraction data revealing several possible relatives of atoms in the crystal structure. With regards to the bpy rings, the structure can be interpreted as two pyridyl rings with coplanar configurations within a unit cell (configuration 1), a twisted bpy ring conformation in which orthogonal pyridyl rings have C4 symmetry about the Cu2+ ion (configuration 2), and a twisted bpy ring conformation in which the two orthogonal pyridyl rings are facing one another within a unit cell (configuration 3). Further, the equatorial fluorine atoms can be positioned such that all atoms are eclipsed with the square grid (position A), oriented at a 21.3 angle with respect to the square grid (position B), and oriented at a 45 angle with respect to the square grid (position C). It was observed that experimental data for CO2 sorption were only consistent with sorption into configurations 1 and 3 with any of the possible equatorial fluorine atom positions at ambient temperatures, although simulations using position A produced slightly higher uptakes in these bpy ring configurations. It is demonstrated that the orientation of the bpy rings in configurations 1 and 3 allows more space for the sorbate molecules and thus promotes favorable MOM-sorbate interactions, resulting in isotherms in line with the experimental results. The results from this study suggests that [Cu(bpy)2SiF 6] in either configuration 1 or 3 with CO2 present in the pores at ambient temperatures is consistent with experimental sorption measurements and crystal structure data. © 2013 American Chemical Society.
Citation:
Forrest KA, Pham T, Nugent P, Burd SD, Mullen A, et al. (2013) Examining the Effects of Different Ring Configurations and Equatorial Fluorine Atom Positions on CO 2 Sorption in [Cu(bpy) 2 SiF 6 ] . Crystal Growth & Design 13: 4542–4548. Available: http://dx.doi.org/10.1021/cg401034s.
Publisher:
American Chemical Society (ACS)
Journal:
Crystal Growth & Design
KAUST Grant Number:
FIC/2010/06
Issue Date:
2-Oct-2013
DOI:
10.1021/cg401034s
Type:
Article
ISSN:
1528-7483; 1528-7505
Sponsors:
This work was supported by the National Science Foundation (Award No. CHE-1152362). Computations were performed under a XSEDE Grant (No. TG-DMR090028) to B.S. This publication is also based on work supported by Award No. FIC/2010/06, made by King Abdullah University of Science and Technology (KAUST). The authors also thank the Space Foundation (Basic and Applied Research) for partial support. The authors acknowledge the use of the services provided by Research Computing at the University of South Florida.
Appears in Collections:
Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorForrest, Katherine A.en
dc.contributor.authorPham, Tonyen
dc.contributor.authorNugent, Patricken
dc.contributor.authorBurd, Stephen D.en
dc.contributor.authorMullen, Ashleyen
dc.contributor.authorWojtas, Lukaszen
dc.contributor.authorZaworotko, Michael J.en
dc.contributor.authorSpace, Brianen
dc.date.accessioned2016-02-25T13:17:42Zen
dc.date.available2016-02-25T13:17:42Zen
dc.date.issued2013-10-02en
dc.identifier.citationForrest KA, Pham T, Nugent P, Burd SD, Mullen A, et al. (2013) Examining the Effects of Different Ring Configurations and Equatorial Fluorine Atom Positions on CO 2 Sorption in [Cu(bpy) 2 SiF 6 ] . Crystal Growth & Design 13: 4542–4548. Available: http://dx.doi.org/10.1021/cg401034s.en
dc.identifier.issn1528-7483en
dc.identifier.issn1528-7505en
dc.identifier.doi10.1021/cg401034sen
dc.identifier.urihttp://hdl.handle.net/10754/598267en
dc.description.abstractSimulations of CO2 sorption were performed in a metal-organic material (MOM) that is part of a "SIFSIX" family of compounds that has remarkable carbon dioxide capture and separation properties. The MOM considered here has the formula [Cu(bpy)2SiF6] (bpy = 4,4′-bipyridine). This hydrophobic MOM is both water-stable and CO 2-specific with significant sorption capacity under ambient conditions. The crystal structure reveals bpy rings and equatorial fluorine atoms in multiple possible orientations; the static disorder has been modeled based on single-crystal X-ray diffraction data revealing several possible relatives of atoms in the crystal structure. With regards to the bpy rings, the structure can be interpreted as two pyridyl rings with coplanar configurations within a unit cell (configuration 1), a twisted bpy ring conformation in which orthogonal pyridyl rings have C4 symmetry about the Cu2+ ion (configuration 2), and a twisted bpy ring conformation in which the two orthogonal pyridyl rings are facing one another within a unit cell (configuration 3). Further, the equatorial fluorine atoms can be positioned such that all atoms are eclipsed with the square grid (position A), oriented at a 21.3 angle with respect to the square grid (position B), and oriented at a 45 angle with respect to the square grid (position C). It was observed that experimental data for CO2 sorption were only consistent with sorption into configurations 1 and 3 with any of the possible equatorial fluorine atom positions at ambient temperatures, although simulations using position A produced slightly higher uptakes in these bpy ring configurations. It is demonstrated that the orientation of the bpy rings in configurations 1 and 3 allows more space for the sorbate molecules and thus promotes favorable MOM-sorbate interactions, resulting in isotherms in line with the experimental results. The results from this study suggests that [Cu(bpy)2SiF 6] in either configuration 1 or 3 with CO2 present in the pores at ambient temperatures is consistent with experimental sorption measurements and crystal structure data. © 2013 American Chemical Society.en
dc.description.sponsorshipThis work was supported by the National Science Foundation (Award No. CHE-1152362). Computations were performed under a XSEDE Grant (No. TG-DMR090028) to B.S. This publication is also based on work supported by Award No. FIC/2010/06, made by King Abdullah University of Science and Technology (KAUST). The authors also thank the Space Foundation (Basic and Applied Research) for partial support. The authors acknowledge the use of the services provided by Research Computing at the University of South Florida.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleExamining the Effects of Different Ring Configurations and Equatorial Fluorine Atom Positions on CO 2 Sorption in [Cu(bpy) 2 SiF 6 ]en
dc.typeArticleen
dc.identifier.journalCrystal Growth & Designen
dc.contributor.institutionUniversity of South Florida Tampa, Tampa, United Statesen
kaust.grant.numberFIC/2010/06en
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.