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Overview of granted projects - Part I

Synthesis and optoelectronic characterization of metal-organic frameworks consisting of
oligo(phenyleneethynylene)s and metal oxo clusters

 

        Consortium:

        Professor Dr. Peter Behrens, Hannover
        Leibniz University Hannover
        Institute of Inorganic Chemistry B

        Professor Dr. Adelheid Godt, Bielefeld
        University of Bielefeld
        Institute of Organic Chemistry II

        Professor Dr. Michael Wark, Bochum
        Ruhr University of Bochum
        Department of Chemistry and Biochemistry
        Chair of Industrial Chemistry

        Project:

        Synthesis and optoelectronic characterization of metal-organic frameworks consisting of oligo
        (phenyleneethynylene)s and metal oxo clusters

        Abstract:

        The aim of this project is to characterize the optoelectronic properties of specifically designed metal-organic frameworks (MOFs) with the vision to employ them in solar cells. For this purpose, oligo(phenyleneethynylene)s (oligoPEs) and related compounds shall be used as linkers between oxo-clusters of Zn, Ti, and Zr, thereby generating porous materials. The available pore space will be used to integrate sensitizing dyes and the electrolyte redox system. The optoelectronic properties of both building units - oligoPE and metal-oxo clusters - will be trimmed, namely through deliberate variations of the oligoPEs (length, substituents, heterocycles) and through inorganic synthesis design providing oxo-clusters of different size and geometry. The optical properties will be analyzed by UV-vis absorption and luminescence spectroscopy. To form active layers for solar cells, the MOFs will be coated onto suitable substrates and optoelectronic properties as photo-current, electron lifetime, and electron transit time will be measured. The unique regular arrangement of the interacting entities in MOFs will allow for a better understanding of how to optimise the factors that influence solar cell efficiency.

        Results:

        Within the project, a large variety of MOFs containing oligo(phenyleneethynylene) (oligoPEs) linkers have been prepared and characterized. Especially interesting are Zr-based MOFs. Here, the application of a modulator approach, i.e. the addition of monocarboxylic acids, has allowed to control the crystal size of the materials, ranging from nanocrystals to single crystals. In this way, the first single crystal X-ray study of a MOF of the UiO-68 topology became feasible (left). Furthermore, a series of porous interpenetrated zirconium-organic frameworks was discovered using oligoPE linkers. The topology of the frameworks is the same as in the UiO-type Zr MOFs (right). The interpenetration still leaves ample free pore space. The materials are thermally stable and can be synthesized with a wide variety of different linkers, containing side chains with different chemical make-up.

        Publications:

        Andreas Schaate, Miriam Schulte, Michael Wiebcke ,Adelheid Godt ,Peter Behrens
        "One-dimensional Zn(II) oligo(phenyleneethynylene)dicarboxylate coordination polymers: Synthesis, crystal structures, thermal and photoluminescent properties"
        Inorganica Chimica Acta 362 (2009) 3600–3606

         

        A. Schaate, P. Roy, A. Godt, J. Lippke, F. Waltz, M. Wiebcke, P. Behrens
        "Modulated Synthesis of Zr-Based Metal-Organic Frameworks: From Nano to Single Crystals"
        Chem. Eur. J. 17 (2011) 6643-6641. DOI: 10.1002/chem.201003211
         

         

        A. Schaate, P. Roy, T. Preuße, S.J. Lohmeier, A. Godt, P. Behrens
        "Porous interpenetrated zirconium-organic frameworks (PIZOFs), a chemically versatile family of MOFs"
        Chem. Eur. J. 17 (2011) 9320-9325. DOI: 10.1002/chem.201101015
         
 
 

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