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Issue 26, 2018
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Synthesis and characterization of a flexible metal organic framework generated from MnIII and the 4,4′-bipyrazolate-ligand

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Abstract

The synthesis and crystal structure of a novel metal organic framework, constructed from MnIII, the 4,4′-bipyrazolate (BPZ) ligand and bridging hydroxyl groups is presented in this work. The network topology is identical to M-CFA-6 (M = Fe, Ga), but in the case of Mn-CFA-6, the structure crystallizes in the monoclinic crystal system due to the Jahn–Teller effect of the high spin d4 manganese(III) centers. Thermal treatment of Mn-CFA-6 leads to decomposition of the framework above 150 °C. The porosity of Mn-CFA-6 was measured by carbon dioxide sorption, since solvent exchange and removal of the occluded solvent molecules leads to a compression of the pores. Electronic spectra of Mn-CFA-6 reveal two distinct absorption bands that are assigned to the two different manganese(III) centers as revealed by the single crystal structure analysis. Furthermore, SQUID measurements exhibit ferromagnetic behaviour of Mn-CFA-6 below the magnetic ordering at 45 K and antiferromagnetic coupling above this temperature. Evaluation of the paramagnetic region by the Curie-Weiß formula reveals an effective moment of 4.8μB, which is very close to the spin-only value of MnIII centers.

Graphical abstract: Synthesis and characterization of a flexible metal organic framework generated from MnIII and the 4,4′-bipyrazolate-ligand

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Publication details

The article was received on 27 Mar 2018, accepted on 04 Jun 2018 and first published on 08 Jun 2018


Article type: Paper
DOI: 10.1039/C8DT01185K
Citation: Dalton Trans., 2018,47, 8779-8786
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    Synthesis and characterization of a flexible metal organic framework generated from MnIII and the 4,4′-bipyrazolate-ligand

    S. Spirkl, M. Grzywa and D. Volkmer, Dalton Trans., 2018, 47, 8779
    DOI: 10.1039/C8DT01185K

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