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TU Dresden » Fakultät Mathematik und Naturwissenschaften » Fachrichtung Chemie und Lebensmittelchemie » Metal-Organic Frameworks
Overview of granted projects - Part I

Host - guest interactions and magnetic ordering in MOFs studied by electron
and nuclear spin resonance spectroscopy

 

        Consortium:

        Dr. Marko Bertmer, Leipzig
        University of Leipzig
        Department of Physics and Geosciences
        Chair of Experimental Physics

        Professor Dr. Martin Hartmann, Erlangen
        Erlangen Catalysis Resource Center

        Professor Dr. Andreas Pöppl, Leipzig
        University of Leipzig
        Department of Physics and Geosciences
        Chair of Experimental Physics

        Project:

        Host - guest interactions and magnetic ordering in MOFs studied by electron and nuclear spin resonance spectroscopy

        Abstract:

        The project is devoted to the study of host-guest interactions in metal-organic framework (MOF) compounds with collaborative magnetic ordering by pulsed electron spin resonance (ESR) and nuclear spin resonance (NMR) spectroscopy. The huge structural variety of MOFs with paramagnetic transition metal ions offer the potential to develop tailor-made low-density porous magnetic materials which can be exploited as magnetic sensors and intelligent multifunctional materials. The obvious advantage of “magnetic MOFs” in comparison with conventional magnetic solids is the opportunity to tune their magnetic properties by adsorption of suitable guest molecules. In order to utilize this advantage in applied material science, a detailed understanding of the electronic and magnetic interaction between the magnetic framework and the adsorbed molecules on a molecular scale is an indispensable prerequisite for the development of such systems. Therefore, advanced ESR and NMR spectroscopic methods will be applied to explore the specific location of the guests and their interaction with the MOF framework as well as the geometrical and electronic structure of the resulting adsorption complexes.

        Results:

        Cu3(btc)2, also known as HKUST-1, is one of the first and best investigated metal organic framework (MOF). We synthesized a hetero-binuclear Cu3(btc)2 where 1 % of the Cu(II) ions in the paddle wheel units are substituted by Zn(II) ions. The formation of mixed Cu/Zn paddle wheel units could be confirmed by electron paramagnetic (EPR) and nuclear magnetic resonance (NMR) spectroscopy. The EPR spectra of the as synthesized and dehydrated material as well as of Cu2.97Zn0.03(btc)2 with adsorbed CH3OH show the change in the coordination sphere of the copper centers from square planar in the dehydrated material to square pyramidal when polar donor molecules are adsorbed.

        Publications:

        Bettina Jee, Dieter Himsl, Maik Icker, Martin Hartmann und Andreas Pöppl
        "Untersuchungen zur chemischen Stabilität von Cu3(btc)2 (HKUST-1)durch N2-Adsorption, Röntgenpulverdiffraktometrie und EPR-Spektroskopie"
        Chemie Ingenieur Technik 2010, 82, No. 7, 1025-1029
         

         

        		 Bettina Jee, Konrad Eisinger, Farhana Gul-E-Noor, Marko Bertmer, Martin Hartmann, Dieter Himsl, and Andreas Pöppl
        "Continuous Wave and Pulsed Electron Spin Resonance Spectroscopy of Paramagnetic Framework Cupric Ions in the Zn(II) Doped Porous Coordination Polymer Cu3-xZnx(btc)2"
        J. Phys. Chem. C 2010, 114, 16630–16639
         

         

        		 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.
         

         

        		 D. Himsl, D. Wallacher, M. Hartmann
        "Improvement of the Hydrogen Adsorption Properties of a Hydroxyl-modified MIL-53(Al) Structural Analogue by Li Doping"
        Angew. Chem. Int. Ed. 2009, 48, 4639-4642.
         

         

        		 M. Meilikhov, K. Yusenko, A. Torrisi, B. Jee, C. Mellot-Draznieks, A. Pöppl, R. A. Fischer
        "Reduction of a Metal–Organic Framework by an Organometallic Complex: Magnetic Properties and Structure of the Inclusion Compound [(η5- C5H5)2Co]0.5@MIL- 47(V)"
        Angew. Chem. Int. Ed. 2010, 49, 6212-6215
         

         

        		 Bettina Jee,Kathrin Koch, Lutz Moschkowitz, Dieter Himsl, Martin Hartman, and Andreas Pöppl
        "Electron Spin Resonance Study of Nitroxide Radical Adsorption at Cupric Ions in the Metal-Organic Framework Compound Cu3(btc)2"
        J. Phys. Chem. Lett. 2011, 2, 357–361
         
 
 

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