Issue 2, 2015

Fe/Ga-CFA-6 – metal organic frameworks featuring trivalent metal centers and the 4,4′-bipyrazolyl ligand

Abstract

The synthesis and crystal structures of the new porous coordination polymers M-CFA-6 (M = Ga, Fe) are described. The structure motif of the M-CFA-6 framework (termed Coordination Framework Augsburg University-6, CFA-6) is closely related to that of the MIL-53 due to its octahedrally coordinated metal centers, bridging hydroxyl groups and the bifunctional 4,4′-bipyrazolyl ligand. Structural properties of the compounds were obtained via XRPD and single-crystal diffraction methods. Ga-CFA-6 and Fe-CFA-6 are isomorphous and crystallize in the orthorhombic crystal system within the space group Imma (no. 74), with the following unit cell parameters: Ga-CFA-6, a = 14.8281(16) Å, b = 6.4872(5) Å, c = 11.3503(12) Å, V = 1091.82(19) Å3; Fe-CFA-6·0.6DMAc, a = 14.8424(19) Å, b = 6.6238(9) Å, c = 11.7467(18) Å, V = 1154.9(3) Å3. Coordination polymers M-CFA-6 were characterized by elemental and thermogravimetric analyses. Variable temperature powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy and BET measurements confirmed the stability of the frameworks up to 250 and 300 °C (Ga-CFA-6 and Fe-CFA-6, respectively) and the porous characters of these compounds. The connectivity of the framework and symmetry of the space group were confirmed by MAS-NMR spectroscopy of Ga-CFA-6. Mössbauer spectroscopy and magnetic measurements were applied to determine the oxidation state of the iron centers in Fe-CFA-6.

Graphical abstract: Fe/Ga-CFA-6 – metal organic frameworks featuring trivalent metal centers and the 4,4′-bipyrazolyl ligand

Supplementary files

Article information

Article type
Paper
Submitted
31 iyl 2014
Accepted
07 okt 2014
First published
08 okt 2014
This article is Open Access
Creative Commons BY-NC license

CrystEngComm, 2015,17, 313-322

Author version available

Fe/Ga-CFA-6 – metal organic frameworks featuring trivalent metal centers and the 4,4′-bipyrazolyl ligand

S. Spirkl, M. Grzywa, C. S. Zehe, J. Senker, S. Demeshko, F. Meyer, S. Riegg and D. Volkmer, CrystEngComm, 2015, 17, 313 DOI: 10.1039/C4CE01583E

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