An Isoreticular Family of Microporous Metal–Organic Frameworks Based on Zinc and 2-Substituted Imidazolate-4-amide-5-imidate: Syntheses, Structures and Properties

Authors

  • Franziska Debatin,

    1. Institut für Chemie, Anorganische Chemie, Universität Potsdam, Karl-Liebknecht-Straße 24-25, 14476 Potsdam (Germany), Fax: (+49) 331-977-5055
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  • Karsten Behrens,

    1. Institut für Chemie, Anorganische Chemie, Universität Potsdam, Karl-Liebknecht-Straße 24-25, 14476 Potsdam (Germany), Fax: (+49) 331-977-5055
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  • Dr. Jens Weber,

    1. Abteilung für Kolloidchemie, Max Planck Institut für Kolloid- und Grenzflächenforschung, 14476 Potsdam (Germany)
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  • Dr. Igor A. Baburin,

    1. Technische Universität Dresden, Institut für Physikalische Chemie und Elektrochemie, 01062 Dresden (Germany)
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  • Prof. Dr. Arne Thomas,

    1. Institut für Chemie, Fakultät II, Technische Universität Berlin, 10623 Berlin (Germany)
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  • Dr. Johannes Schmidt,

    1. Institut für Chemie, Fakultät II, Technische Universität Berlin, 10623 Berlin (Germany)
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  • Dr. Irena Senkovska,

    1. Anorganische Chemie, Chemie und Lebensmittelchemie, Technische Universität Dresden, 01062 Dresden (Germany)
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  • Prof. Dr. Stefan Kaskel,

    1. Anorganische Chemie, Chemie und Lebensmittelchemie, Technische Universität Dresden, 01062 Dresden (Germany)
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  • Alexandra Kelling,

    1. Institut für Chemie, Anorganische Chemie, Universität Potsdam, Karl-Liebknecht-Straße 24-25, 14476 Potsdam (Germany), Fax: (+49) 331-977-5055
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  • Dr. Niklas Hedin,

    1. Department of Materials and Environmental Chemistry and the Berzelii Centre EXSELENT on Porous Materials, Arrhenius Laboratory, Stockholm University, 10691 Stockholm (Sweden)
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  • Dr. Zoltan Bacsik,

    1. Department of Materials and Environmental Chemistry and the Berzelii Centre EXSELENT on Porous Materials, Arrhenius Laboratory, Stockholm University, 10691 Stockholm (Sweden)
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  • Dr. Stefano Leoni,

    1. Technische Universität Dresden, Institut für Physikalische Chemie und Elektrochemie, 01062 Dresden (Germany)
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  • Prof. Dr. Gotthard Seifert,

    1. Technische Universität Dresden, Institut für Physikalische Chemie und Elektrochemie, 01062 Dresden (Germany)
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  • Prof. Dr. Christian Jäger,

    1. BAM Federal Institute for Materials Research and Testing, 12489 Berlin (Germany)
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  • Dr. Christina Günter,

    1. Institut für Erd- und Umweltwissenschaften, Universität Potsdam, 14476 Potsdam (Germany)
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  • Prof. Dr. Uwe Schilde,

    1. Institut für Chemie, Anorganische Chemie, Universität Potsdam, Karl-Liebknecht-Straße 24-25, 14476 Potsdam (Germany), Fax: (+49) 331-977-5055
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  • Dr. Alwin Friedrich,

    1. Institut für Chemie, Anorganische Chemie, Universität Potsdam, Karl-Liebknecht-Straße 24-25, 14476 Potsdam (Germany), Fax: (+49) 331-977-5055
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  • Prof. Dr. Hans-Jürgen Holdt

    Corresponding author
    1. Institut für Chemie, Anorganische Chemie, Universität Potsdam, Karl-Liebknecht-Straße 24-25, 14476 Potsdam (Germany), Fax: (+49) 331-977-5055
    • Institut für Chemie, Anorganische Chemie, Universität Potsdam, Karl-Liebknecht-Straße 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 Å), 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 (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 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-1–4 under dry conditions and that both CO2 and H2O are physisorbed on IFP-1 under moist conditions.

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