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Overview of granted projects - Part I

Targeting selective host-guest interactions in functionalized MOFs –
synthesis, NMR-studies and sensor design



        Professor Dr. Thomas Bein, München
        Ludwig Maximilian University of München
        Department of Chemistry and Biochemistry
        Chair of Physical Chemistry

        Professor Dr. Jürgen Senker, Bayreuth
        University of Bayreuth
        Department of Chemistry and Biochemistry
        Chair of Inorganic Chemistry III

        Professor Dr. Norbert Stock, Kiel
        Christian Albrecht University of Kiel
        Institute of Inorganic Chemistry


        Targeting selective host-guest interactions in functionalized MOFs – synthesis, NMR-studies and sensor design


        The goal of this collaborative project is to develop functionalized MOFs with controlled hostguest interactions for the design of selective chemical sensors. Metal-organic frameworks offer an enormous space of structural and interaction parameters for the control of molecular host-guest interactions, ranging from the pore size, shape, and topology to specific local molecular interactions between guest molecules and the porous framework. We wish to introduce functionality into the pore structure of MOFs using modified linker groups or postsynthesis modification. Synthetic high-throughput methods, including microwave techniques, will allow us to generate the functionalized structures with high efficiency. Modern solid-state NMR techniques such as homo- and heteronuclear zero- or multi-quantum correlation spectroscopy will be used to unravel specific interactions and mobility. These insights will enable a targeted design of tailored functionalities. Selected examples of hosts featuring highly specific host-guest binding will be grown in the form of nanoscale porous thin films for the construction of chemical sensors. Both mass-based piezoelectric sensors exploiting selective adsorption isotherm behavior and fluorescence-based optical sensors relying on specific spectral changes will be developed.


        Figure 1

        Figure 2


        Figure 3


        We have succeeded in the synthesis of various –NH2 functionalized MOFs such as CAU-1-NH2 (Figure 1), CAU-3-NH2, Al-MIL53-NH2, Al-MIL-101-NH2 and Cr-MIL-101-NH2. Post-synthetic modification using acid anhydrides and alkylisocyanates was shown to be successful systems. The functionalisation was confirmed by solid state NMR-spectroscopy (Figure 2) which also allowed us to determine the arrangement of the functional groups as well as host guest interactions. In addition, the growth of HKUST-1 was investigated by in-situ AFM methods, and thin-film growth techniques were developed and applied that allowed us the oriented growth of various MOFs, e.g., Fe-MIL-88-NH2 and CAU-1-NH2 (Figure 3). These films were characterized by sorption measurements using a quartz crystal microbalance and the influence of functional groups on the sorption properties was demonstrated


        Enrica Biemmi, Camilla Scherb, and Thomas Bein
        "Oriented Growth of the Metal Organic Framework Cu3(BTC)2(H2O)3.xH2O Tunable with Functionalized Self-Assembled Monolayers"

        J. AM. CHEM. SOC. 2007, 129, 8054-8055


        Camilla Scherb, Alexander Schödel, and Thomas Bein
        "Directing the Structure of Metal–Organic Frameworks by Oriented Surface Growth on an Organic Monolayer"

        Angew. Chem. Int. Ed. 2008, 47, 5777 –5779


        Neena S. John, Camilla Scherb, Maryiam Shöâeè ,Michael W. Anderson, Martin P. Attfield and Thomas Bein
        "Single layer growth of sub-micron metal–organic framework crystals observed by in situ atomic force microscopy"
        Chem. Commun., 2009, 6294–6296


        Tim Ahnfeldt, Nathalie Guillou, Daniel Gunzelmann, Irene Margiolaki, Thierry Loiseau, Gérard Férey, Jürgen Senker, and Norbert Stock
        "[AI4(OH)2(OCH3)4(H2N-bdc)3]·xH2O: A 12-Connected Porous Metal–Organic Framework with an Unprecedented Aluminum-Containing Brick"

        Angew. Chem. 2009, 121, 5265–5268


        Andreas Sonnauer, Frank Hoffmann, Michael Fröba, Lorenz Kienle, Viola Duppel, Matthias Thommes, Christian Serre, Gérard Férey, and Norbert Stock
        "Giant Pores in a Chromium 2,6-Naphthalenedicarboxylate Open-Framework Structure with MIL-101 Topology"

        Angew. Chem. 2009, 121, 3849 –3852


        Tim Ahnfeldt, Daniel Gunzelmann, Thierry Loiseau,Dunja Hirsemann,Jürgen Senker, Gérard Férey,and Norbert Stock
        "Synthesis and Modification of a Functionalized 3D Open-Framework Structure with MIL-53 Topology"

        Inorganic Chemistry, Vol. 48, No. 7, 2009, 3057-3064


        M. Mendt, B. Jee, N. Stock, T. Ahnfeldt, M. Hartmann, D. Himsl, A. Pöppl
        "Structural Phase Transitions and Thermal Hysteresis in the Metal-Organic Framework Compound MIL-53 As Studied by Electron Spin Resonance Spectroscopy"

        J. Phys. Chem. C 2010, 114, 19443-19451


        S. Bernt, V. Guillerm, C. Serre, N. Stock
        "Direct covalent post-synthetic chemical modification of Cr-MIL-101 using nitrating acid"

        Chem. Commun. 2011, DOI: 10.1039/C0CC04526H


        T. Ahnfeldt, J. Moellmer, V. Guillerm, R. Staudt, C. Serre, N. Stock
        "High-throughput and time-resolved EDXRD Study of the Formation of CAU-1-(OH)2 – Microwave and Conventional Heating"

        Chem. Eur. J. 2011, accepted


        M. Plabst, R. Kohn, T. Bein
        "The influence of the guest ion on the synthesis and sorption properties of an open framework lanthanide tetrakisphosphonate"

        CrystEngComm 2010, 12, 1920


        M. Plabst, L. B. McCusker, T. Bein
        "Exceptional Ion-Exchange Selectivity in a Flexible Open Framework Lanthanum(III)tetrakisphosphonate"

        Journal of the American Chemical Society 2009, 131, 18112


        F. Hinterholzinger, C. Scherb, T. Ahnfeldt, N. Stock, T. Bein
        "Oriented growth of the functionalized metal-organic framework CAU-1 on -OH- and -COOH-terminated self-assembled monolayers"

        Physical Chemistry Chemical Physics 2010, 12, 4515.


        A. Schoedel, C. Scherb, T. Bein
        "Oriented Nanoscale Films of Metal–Organic Frameworks By Room-Temperature Gel-Layer Synthesis"

        Angew. Chem. Int. Ed. 2010, 49, 7225.


        C. Scherb, R. Koehn, T. Bein
        "Sorption behavior of an oriented surface-grown MOF-film studied by in situ X-ray diffraction"

        Journal of Materials Chemistry 2010, 20, 3046







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