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Overview of granted projects - Part II

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

 

        Consortium:

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

        Professor Dr. Bettina Valeska Lotsch, München
        Ludwig Maximilian University of München
        Department of Chemistry and Biochemistry
        Chair of Inorganic Chemistry

        Professor Dr. Ulrich Lüning, Kiel
        Christian Albrecht University of Kiel
        Otto Diels Institute of Organic 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

        Project:

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

        Abstract:

        Metal-organic frameworks represent a highly versatile class of porous materials whose interactions with guest molecules can be controlled, in principle, by varying the nature of the organic linker molecules as well as the coordination environment of the constituting metal ions. This project aims at the understanding and control of host-guest interactions in MOFs, which will be achieved through functionalization of the organic linker molecules. Introducing well-positioned specific functionalities is anticipated to provide a number of important advantages including the variation of host-guest interactions in the same class of MOFs with similar overall properties and the ability to design selective interactions independent from the construction of the host lattice. Based on results of the first funding period, the project will concentrate on anchors with double and triple hydrogen bond patterns found in nature. They provide lock-key interactions with important biomolecules like nucleobases and barbiturates. By this it is anticipated to built-up a series of promising receptors for sensor studies. The partners in this consortium all bring complementary skills and background to the project, ranging from synthesis of molecular building blocks to the synthesis and functionalization of new MOF structures, the detailed physicochemical study of molecular host-guest interactions, to the growth and investigation of novel MOF-based thin films and MOF-based Bragg stacks, which will be explored as the basis for novel concepts in selective chemical sensing.

        Results:

        Figure 1

         

        We have recently developed a novel strategy for the room temperature growth of oriented nanoscale films of metal-organic frameworks by using the concept of gel-layer synthesis (Fig. 1). This approach is based on the storage of one reaction partner for framework synthesis in a polymer gel layer, followed by diffusion of the other reaction partner into the gel layer and to a nucleation interface provided by a functionalized self-assembled monolayer (SAM). The gel-layer synthesis was successfully applied for different MOFs [A. Schoedel, C. Scherb, T. Bein, Angew. Chem. Int. Ed. 2010, 49, 7225].

         

        Figure 2

         

        Mesoporous amino-functionalized MOF thin films with the UiO-68 topology were grown in a highly oriented fashion on two different self-assembled monolayers on gold. The oriented MOF films were covalently modified with the fluorescent dye Rhodamine B inside the pore system (Fig. 2), as demonstrated with size-selective fluorescence quenching studies. Our study suggests that mesoporous metal–organic frameworks are promising hosts for the covalent attachment of numerous functional moieties in a molecularly designed crystalline environment. We anticipate that mesoporous UiO-68–NH2 thin films will offer a versatile platform for precisely designing various host–guest interactions within a stable pore system featuring a well-defined molecular framework [F. M. Hinterholzinger, S. Wuttke, P. Roy, T. Preuße, A. Schaate, P. Behrens, A. Godt and T. Bein, Dalton Trans. 2012, 41, 3899].

         

        Figure 3

         

        We have investigated the fabrication of one-dimensional photonic crystals (Bragg stacks) based on the metal-organic framework ZIF-8 and mesoporous TiO2 via two complementary bottom-up synthesis approaches. The combination of textural mesoporosity arising from the nanoparticle-based layers with inherent microporosity provided by the ZIF imparts molecular selectivity and at the same time guarantees molecular diffusion within the Bragg stack. The uptake of guest species into the porous layers induces a change of the optical thickness of the multilayer and, hence, is translated into a readable optical signal. The analyte sorption behavior was studied as a function of partial pressure of various alcohols, demonstrating that the Bragg stacks are sensitive and selective with respect to the different solvent vapors (Fig. 3). We expect that the concept of MOF-based photonic architectures will provide a versatile platform for future selective, label-free optical sensors owing to the great variety and inherent tunability of MOFs [F. M. Hinterholzinger, A. Ranft, H. Feckl, T. Bein and B. V. Lotsch, J. Mater. Chem. 2012, 22, 101356].

        Publications:

        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.
         

         

        C. Scherb, J. J. Williams, F. M. Hinterholzinger, S. Bauer, N. Stock, T. Bein
        "Implementing chemical functionality into oriented ?lms of metal–organic frameworks on self-assembled monolayers"
        J. Mater. Chem. 2011, 21, 14849-14856.
         

         

        F. M. Hinterholzinger, S. Wuttke, P. Roy, T. Preuße, A. Schaate, P. Behrens, A. Godt, T. Bein
        "Highly oriented surface-growth and covalent dye labeling of mesoporous metal–organic frameworks"
        Dalton Trans. 2012, 41, 3899-3901.
         

         

        E. A. Flügel, A. Ranft, F. Haase, B. V. Lotsch
        "Synthetic routes toward MOF nanomorphologies"
        J. Mater. Chem. 2012, 22, 10119-10133.
         

         

        F. M. Hinterholzinger, A. Ranft, H. Feckl, T. Bein, B. V. Lotsch
        "One-dimensional metal-organic framework photonic crystals used as platforms for vapor sensing"
        J. Mater. Chem. 2012, 22, 10356-10362.
         
 
 

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