M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni) Metal-Organic Frameworks Exhibiting Increased Charge Density and Enhanced H2 Binding at the Open Metal Sites

Title:
M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni) Metal-Organic Frameworks Exhibiting Increased Charge Density and Enhanced H2 Binding at the Open Metal Sites
Authors:
Kapelewski, Matthew T.; Geier, Stephen J.; Hudson, Matthew R.; Stück, David; Mason, Jarad A.; Nelson, Jocienne N.; Xiao, Dianne J.; Hulvey, Zeric; Gilmour, Elizabeth; FitzGerald, Stephen; Head-Gordon, Martin; Brown, Craig M.; Long, Jeffrey R.
Abstract:
The well-known frameworks of the type M2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate) have numerous potential applications in gas storage and separations, owing to their exceptionally high concentration of coordinatively unsaturated metal surface sites, which can interact strongly with small gas molecules such as H2. Employing a related meta-functionalized linker that is readily obtained from resorcinol, we now report a family of structural isomers of this framework, M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni; m-dobdc4– = 4,6-dioxido-1,3-benzenedicarboxylate), featuring exposed M2+ cation sites with a higher apparent charge density. The regioisomeric linker alters the symmetry of the ligand field at the metal sites, leading to increases of 0.4–1.5 kJ/mol in the H2 binding enthalpies relative to M2(dobdc). A variety of techniques, including powder X-ray and neutron diffraction, inelastic neutron scattering, infrared spectroscopy, and first-principles electronic structure calculations, are applied in elucidating how these subtle structural and electronic differences give rise to such increases. Importantly, similar enhancements can be anticipated for the gas storage and separation properties of this new family of robust and potentially inexpensive metal–organic frameworks.
Citation:
Kapelewski, M.T., S.J. Geier, M.R. Hudson, et al. 2014. "M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni) Metal-Organic Frameworks Exhibiting Increased Charge Density and Enhanced H2 Binding at the Open Metal Sites.” Journal of the American Chemical Society 136(34): 12119-12129.
Publisher:
American Chemical Society
DATE ISSUED:
2014
Department:
Physics and Astronomy
Type:
Article
PUBLISHED VERSION:
10.1021/ja506230r
PERMANENT LINK:
http://hdl.handle.net/11282/566766

Full metadata record

DC FieldValue Language
dc.contributor.authorKapelewski, Matthew T.en
dc.contributor.authorGeier, Stephen J.en
dc.contributor.authorHudson, Matthew R.en
dc.contributor.authorStück, Daviden
dc.contributor.authorMason, Jarad A.en
dc.contributor.authorNelson, Jocienne N.en
dc.contributor.authorXiao, Dianne J.en
dc.contributor.authorHulvey, Zericen
dc.contributor.authorGilmour, Elizabethen
dc.contributor.authorFitzGerald, Stephenen
dc.contributor.authorHead-Gordon, Martinen
dc.contributor.authorBrown, Craig M.en
dc.contributor.authorLong, Jeffrey R.en
dc.date.accessioned2015-08-13T10:33:34Zen
dc.date.available2015-08-13T10:33:34Zen
dc.date.issued2014en
dc.identifier.citationKapelewski, M.T., S.J. Geier, M.R. Hudson, et al. 2014. "M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni) Metal-Organic Frameworks Exhibiting Increased Charge Density and Enhanced H2 Binding at the Open Metal Sites.” Journal of the American Chemical Society 136(34): 12119-12129.en
dc.identifier.issn0002-7863en
dc.identifier.urihttp://hdl.handle.net/11282/566766en
dc.description.abstractThe well-known frameworks of the type M2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate) have numerous potential applications in gas storage and separations, owing to their exceptionally high concentration of coordinatively unsaturated metal surface sites, which can interact strongly with small gas molecules such as H2. Employing a related meta-functionalized linker that is readily obtained from resorcinol, we now report a family of structural isomers of this framework, M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni; m-dobdc4– = 4,6-dioxido-1,3-benzenedicarboxylate), featuring exposed M2+ cation sites with a higher apparent charge density. The regioisomeric linker alters the symmetry of the ligand field at the metal sites, leading to increases of 0.4–1.5 kJ/mol in the H2 binding enthalpies relative to M2(dobdc). A variety of techniques, including powder X-ray and neutron diffraction, inelastic neutron scattering, infrared spectroscopy, and first-principles electronic structure calculations, are applied in elucidating how these subtle structural and electronic differences give rise to such increases. Importantly, similar enhancements can be anticipated for the gas storage and separation properties of this new family of robust and potentially inexpensive metal–organic frameworks.en
dc.language.isoen_USen
dc.publisherAmerican Chemical Societyen
dc.identifier.doi10.1021/ja506230ren
dc.subject.departmentPhysics and Astronomyen
dc.titleM2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni) Metal-Organic Frameworks Exhibiting Increased Charge Density and Enhanced H2 Binding at the Open Metal Sitesen
dc.typeArticleen
dc.identifier.journalJournal of the American Chemical Societyen
dc.subject.keywordIron(II) coordination sitesen_US
dc.subject.keywordCarbon-dioxide captureen_US
dc.subject.keywordHydrogen storageen_US
dc.subject.keywordMethane storageen_US
dc.subject.keywordFunctional theoryen_US
dc.subject.keywordHydrocarbon separationsen_US
dc.identifier.volume136en
dc.identifier.issue34en
dc.identifier.startpage12119en
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