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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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Synthesis and Characterization of Functionalized Metal-organic Frameworks
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Robust Multifunctional Yttrium-Based Metal-Organic Frameworks with Breathing Effect.

Ana D G Firmino1,2, Ricardo F Mendes1, Margarida M Antunes1

  • 1Department of Chemistry, CICECO-Aveiro Institute of Materials, University of Aveiro , 3810-193 Aveiro, Portugal.

Inorganic Chemistry
|January 27, 2017
PubMed
Summary

We synthesized novel yttrium-based metal-organic frameworks (MOFs) with a tetraphosphonate linker using green microwave synthesis. These robust MOFs exhibit a unique breathing effect and show promise as catalysts and proton conductors.

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Area of Science:

  • Materials Science
  • Inorganic Chemistry
  • Crystallography

Background:

  • Metal-organic frameworks (MOFs) offer tunable properties for various applications.
  • Developing stable and functional MOFs with sustainable synthesis methods is crucial.
  • Phosphonate-based MOFs are an emerging class of materials with unique characteristics.

Purpose of the Study:

  • To synthesize and characterize a new family of phosphonate- and yttrium-based MOFs.
  • To investigate the structural flexibility and reversible single-crystal to single-crystal (SC-SC) transformation of these MOFs.
  • To evaluate the performance of the synthesized MOFs as heterogeneous catalysts and proton conductors.

Main Methods:

  • Microwave-assisted synthesis of MOFs using a tetraphosphonic acid linker and Y3+ cations.
  • Structural analysis via X-ray crystallography, thermogravimetry, and variable-temperature X-ray diffraction.
  • Assessment of catalytic activity and proton conductivity through dedicated experimental setups.

Main Results:

  • Four novel MOF compounds, [Y(H5btp)]·5.5H2O (1), [Y(H5btp)]·2.5H2O (2), (H3O)[Y2(H5btp)(H4btp)]·H2O (3), and [Y(H5btp)]·H2O·0.5(MeOH) (4), were successfully synthesized.
  • A remarkable reversible single-crystal to single-crystal (SC-SC) transformation was observed due to solvent loss and gain, without altering the framework topology.
  • Compound 2 demonstrated high catalytic efficiency (94% conversion) for benzaldehyde acetalization, while compound 3 exhibited excellent proton conductivity (2.58 × 10-2 S cm-1) at 98% relative humidity.

Conclusions:

  • The synthesized phosphonate- and yttrium-based MOFs represent a stable and thermally robust class of materials.
  • The observed breathing effect and SC-SC transformation highlight the structural adaptability of these MOFs.
  • These MOFs show significant potential for applications in heterogeneous catalysis and proton conduction, facilitated by a sustainable synthesis approach.