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An isoreticular family of microporous metal-organic frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate Syntheses, structures and properties

  • We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-14, IFP=imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R=Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.01.7 angstrom), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and 1H MAS and 13C CP-MAS NMR spectroscopy. All IFPs showed high thermal stability (345400?degrees C); IFP-1 and IFP-4 were stable in boiling water for 7 d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO2We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-14, IFP=imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R=Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.01.7 angstrom), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and 1H MAS and 13C CP-MAS NMR spectroscopy. All IFPs showed high thermal stability (345400?degrees C); IFP-1 and IFP-4 were stable in boiling water for 7 d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO2 was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH4 (at 298 K), CO2 (at 298 K) and H2 (at 77 K) at high pressure were also investigated. In situ IR spectroscopy showed that CO2 is physisorbed on IFP-14 under dry conditions and that both CO2 and H2O are physisorbed on IFP-1 under moist conditions.show moreshow less

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Metadaten
Author:Franziska Debatin, Karsten Behrens, Jens Weber, Igor A. Baburin, Arne Thomas, Johannes Schmidt, Irena Senkovska, Stefan Kaskel, Alexandra Kelling, Niklas Hedin, Zoltan Bacsik, Stefano Leoni, Gotthard Seifert, Christian Jäger, Christina Günter, Uwe SchildeORCiDGND, Alwin Friedrich, Hans-Jürgen Holdt
DOI:https://doi.org/10.1002/chem.201200889
ISSN:0947-6539 (print)
Parent Title (English):Chemistry - a European journal
Publisher:Wiley-VCH
Place of publication:Weinheim
Document Type:Article
Language:English
Year of first Publication:2012
Year of Completion:2012
Release Date:2017/03/26
Tag:N; O ligands; adsorption; metal- organic frameworks; microporous materials; zinc
Volume:18
Issue:37
Pagenumber:11
First Page:11630
Last Page:11640
Funder:Deutsche Forschungsgemeinschaft [SPP-1362]
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Erd- und Umweltwissenschaften
Peer Review:Referiert