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Overview of granted projects - Part II

MOF Based Sorption Sensors by Rare Earth Luminescence

 

        Consortium:

        Dr. Florian Beuerle, Würzburg
        University of Würzburg
        Institute of Organic Chemistry

        Professor Dr. Claus Feldmann, Karlsruhe
        Karlsruhe Institute of Technology
        Institute of Inorganic Chemistry

        Professor Dr. Klaus Müller-Buschbaum, Würzburg
        University of Würzburg
        Institute of Inorganic Chemistry

        Project:

        MOF Based Sorption Sensors by Rare Earth Luminescence

        Abstract:

        The project focuses on a combination of two properties: luminescence and sorption, with their depen-dency rendering a new sensoring for sorption accessible via observation of an emission. In the prelim-inary period it was successfully shown that luminescence can be implemented into Ln-N-MOFs as an intrinsic property leading to the MOFs with the highest quantum efficiencies known today. It was also proven that microporosity is observed in combination with luminescence in the same MOF material and that luminescence can be quenched by certain adsorbants. To improve the selectivity, new MOFs with linkers suitable both as antennas as well as modifiers of the pore systems are aims of the second period. Novel inverse MOFs based on functionalized fullerenes are included in which the organic linker constitutes the connectivity centers interlinked by metal ions. This offers two perspectives: Intrinsic luminescence with improved quenching options upon sorption as well as the inclusion of luminescent nanoparticles into the inverse MOF. Functionalized fullerenes offer nanometer spacing from their own extensions in contrast to conventional MOFs and ZIFs that do not incorporate these particles. Lumi-nescence will be characterized by photoluminescence spectroscopy, quantum yield, decay determina-tions, and porosity utilizing BET and drifting balances for pressures up to 200 bar. Quantification of the dependency luminescence versus sorption to evaluate the sensor effect by simultaneous fluorescence / porosity studies is the final goal of the project.

        Results:

        The MOF system 2∞[Ln2Cl6(bipy)3]·2bipy can be successfully used for an efficient tuning of the emission colour. During MOF formation different ratios of Eu3+ and Tb3+ can be implemented into the MOF by mixing their trichlorides with GdCl3 under solvent free melt conditions of 4,4’-bipyridine, as the three trivalent lanthanides form a series of mixed crystal MOFs. Depending on the ratio of the three lanthanides networks of the formula 2∞[Gd2-x-yEuxTbyCl6(bipy)3]·2bipy, 0.1 ≤ x,y ≤ 0.5 are formed. 4,4’-bipyridine functions as efficient antenna. A perfect series of luminescence tuned hybrid materials can be formed that covers the complete visible spectrum in-between green and red emission including yellow and orange. As Gd3+ is not involved in the radiative processes it can be utilized as a matrix to dilute the two other lanthanide ions within a majority of gadolinium connectivity centers. The materials show multifunctionality as the luminescence is retained during activation of the MOFs for microporous materials.

         

        Photoluminescence of the series of solid solutions 2∞[Gd2-x-yEuxTbyCl6(bipy)3]·2bipy under UV-light (? = 302 nm), 2-8 being arranged in uprising number from left to right.

         
        N2 adsorption isotherms at 77 K for 2∞[Gd2Cl6(bipy)3] in cm3g-1 uptake depending on variation of the activation temperature of the MOF.

         

        		 Aiming at sensor-type features based on nanoparticle-modified MOFs, inorganic-organic hybrids such as the compound ZrO(FMN) (FMN: flavin mononucleotide) have been introduced as novel luminescent nanomaterials. ZrO(FMN) comprises several important benefits, including a quick and easy water-based synthesis, potentially low costs of production, a high biocompatibility, and a variable concentration of the incorporated dye, for allowing quasi-infinite number of luminescent centers. Typical key-issues for quantum dots as well as metal-doped nanoparticles, such as high-temperature crystallization and core-shell type surface conditioning, do not need any consideration, here. Metal-doped oxides materials (e.g. LaPO4:Ce,Tb, CaF2:Ce,Tb, YVO4:Eu or Zn2SiO4:Mn) that we have also proposed for incorporation into MOFs by nature comprise several of the above listed disadvantages, too.

         

        ZrO(FMN) – a novel concept of organic-inorganic hybrid luminescent nanomaterials.

         

        		 While introducing the concept of dye-modified zirconium phosphates (DMZP’s) as an alternative class of luminescent nanomaterials, it turned out that these nanomaterials allow for controlled switching of the luminescence. Thus, the green emission of the system ZrO(HPO4)1-x(FMN)x can be reversibly turned on and off. In concrete, the green emission is switched off by reduction, such as in the presence of [S2O4]2-, N2H4 or H2. The emission is switched on by re-oxidation, such as in the presence of O2. Moreover, the emission of the inorganic-organic hybrid nanomaterials can be modified by introducing alternative fluorescent dyes. Thus, the luminescent nanomaterial ZrO(UFP) (UFP: umbelliferonephosphate) shows emission of blue light. First experiments evidence that an incorporation of ZrO(FMN) nanoparticles into MOFs is possible. Next steps will address additional emission colors of the nanoparticles, the incorporation of luminescent nanoparticles in MOFs as well as the controlled switching of the light emission.

         

        		 Exohedrally functionalized fullerene derivatives are investigated regarding their potential as connectivity centers in novel inverse MOFs. This offers two perspectives: Intrinsic luminescence with improved quenching options upon sorption as well as the inclusion of luminescent nanoparticles into the inverse MOF. Functionalized fullerenes offer nanometer spacing from their own extensions in contrast to conventional MOFs and ZIFs that do not incorporate these particles.

         


        Publications:

        P.R. Matthes, C. J. Höller, M. Mai, J. Heck, S. J. Sedlmaier, S. Schmiechen, C. Feldmann, W. Schnick, K. Müller-Buschbaum
        "Luminescence tuning of MOFs via ligand to metal and metal to metal energy transfer by co-doping of MOF-Conversion from 2∞[Gd2Cl6(bipy)3] 2bipy with europium and terbium"
        J. Mater. Chem. 2012, 22, 10179.

         

         

        A. Zurawski, J.-C. Rybak, L. V. Meyer, P. R. Matthes, V. Stepanenko, N. Dannenbauer, F. Würthner, K. Müller-Buschbaum
        "Alkaline earth imidazolate coordination polymers by solvent free melt synthesis as potential host lattices for rare earth photoluminescence: x∞[AE(Im)2(ImH)2-3], Mg, Ca, Sr, Ba, x = 1-2"
        Dalton Trans. 2012, 4067.

         

         

        A. Zurawski, M. Mai, D. Baumann, C. Feldmann, K. Müller-Buschbaum
        "Homoleptic Imidazolate Frameworks 3∞[Sr1-xEux(Im)2] - Hybrid Materials with Efficient Tunable Luminescence"
        Chem. Commun. 2011, 47, 496.

         

         

        M. Roming, C. Feldmann
        "Zirconium Umbelliferonephosphate – A Luminescent Organic-Inorganic Hybrid Nanomaterial"
        Solid State Sci. 2011, 13, 508.

         

         

        J.-C. Rybak, C. J. Höller, P. R. Matthes, K. Müller-Buschbaum, M. Mai, C. Feldmann, R. Köhn
        "Steps Towards MOF Based Sorption Sensors by Rare Earth Luminescence"
        Z. Anorg. Allg. Chem. 2010, 636, 2099.

         

         

        J.-C. Rybak, I. Schellenberg, R. Pöttgen, K. Müller-Buschbaum
        "MOFs by Transformation of 1D-Coordination Polymers II: The Homoleptic Divalent Rare Earth 3D-Benzotriazolate 3∞[Eu(Btz)2] Initiating from 1∞[Eu(Btz)2(BtzH)2]"
        Z. Anorg. Allg. Chem. 2010, 636, 1720.

         

         

        A. Zurawski, F. Hintze, K. Müller-Buschbaum
        "Utilizing Metal Melts of Low-Melting Metals as a Novel Approach for MOF Synthesis: The 3D-Imidazolate 3∞[Ga2(Im)6ImH] from Gallium and Imidazole"
        Z. Anorg. Allg. Chem. 2010, 636, 1333.

         

         

        C. J. Höller, K. Müller-Buschbaum
        "Frameworks by Solvent Free Synthesis of Rare Earth Chlorides with Molten 1,3-Benzodintrile and Tailoring of the Particle Size: 3∞[LnCl3(1,3-Ph(CN)2)], Ln = Y, Dy, Ho, Er, Yb"
        Eur. J. Inorg. Chem. 2010, 454.

         

         

        C. J. Höller, M. Mai, C. Feldmann, K. Müller-Buschbaum
        "The Interaction of Rare Earth Chlorides with 4,4'-Bipyridine for the Reversible Formation of Template Based Luminescent Ln-N-MOFs"
        Dalton Trans. 2010, 39, 461.

         

         

        C. J. Höller, P. Matthes, J. Beckmann, K. Müller-Buschbaum
        "MOF Formation vs. Reversible High Ligand Uptake in Anhydrous Halides: Two Opposing Aspects of 3∞[La2Cl6(4,4-bipy)5](4,4-bipy)4"
        Z. Anorg. Allg. Chem. 2010, 636, 395.

         

         

        J.-C. Rybak, M. Tegel, D. Johrendt and K. Müller-Buschbaum
        "Polymorphism of Isotypic Series of Homoleptic 1,2,3-Triazolate MOFs [Ln(Tz*)3] Containing the Heavy Lanthanides Gd-Lu: From Open to Dense Frameworks of Varying Dimensionality"
        Z. Kristallogr. 2010, 225, 187.

         

         

        M. Roming, H. Lünsdorf, K. E. J. Dittmar, C. Feldmann
        "ZrO(HPO4)1-x(FMN)x: Schnelle und einfache Synthese eines nanokaligen Lumineszenzbiomarkers"
        Angew. Chem. 2010, 122, 642.

         

         

        M. Roming, H. Lünsdorf, K. E. J. Dittmar, C. Feldmann
        "ZrO(HPO4)1-x(FMN)x: Quick and Easy Synthesis of a Nanoscale Luminescent Biomarker"
        Angew. Chem. Int. Ed. 2010, 49, 632.

         

         

        H. Goesmann, C. Feldmann
        "Nanopartikuläre Funktionsmaterialien (Review)"
        Angew. Chem. 2010, 122, 1402-1437.

         

         

        H. Goesmann, C. Feldmann
        "Nanoparticulate Functional Materials (Review)"
        Angew. Chem. Int. Ed. 2010, 49, 1362.

         

         

        M. Roming, C. Feldmann
        "Anorganisch-organischer Kompositleuchtstoff"
        Patent application DE 10 2008 009541.9, US 12 867,348, WO 2009 100800 A1.

         
 
 

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