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Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
Synthesis and characterization of a flexible metal organic framework generated from MnIII and the
S Spirkl1, M Grzywa, D Volkmer
1University of Augsburg, Institute of Physics, Chair of Solid State and Materials Chemistry, Universitätsstrasse 1, 86159 Augsburg, Germany. dirk.volkmer@physik.uni-augsburg.de.
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.
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