An Isoreticular Family of Microporous Metal-Organic Frameworks Based on Zinc and 2-Substituted Imidazolate-4-amide-5-imidate: Syntheses, Structures and Properties |
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Authors: | 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 Schilde Alwin Friedrich Hans-Jürgen Holdt |
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Affiliation: | Institut für Chemie, Anorganische Chemie, Universit?t Potsdam, Karl-Liebknecht-Stra?e 24-25, 14476 Potsdam (Germany), Fax: (+49)?331-977-5055. |
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Abstract: | We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-1-4, 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 (4.0-1.7??), 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 (1) H?MAS and (13) C?CP-MAS?NMR spectroscopy. All IFPs showed high thermal stability (345-400?°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 CO(2) was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH(4) (at 298?K), CO(2) (at 298?K) and H(2) (at 77?K) at high pressure were also investigated. In situ IR spectroscopy showed that CO(2) is physisorbed on IFP-1-4 under dry conditions and that both CO(2) and H(2) O are physisorbed on IFP-1 under moist conditions. |
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