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Interpenetrated (8,3)-c and (10,3)-b Metal–Organic Frameworks Based on {Fe(III)3} and {Fe(III)2Co(II)} Pivalate Spin Clusters

Type of publication Peer-reviewed
Publikationsform Original article (peer-reviewed)
Author Botezat Olga, van Leusen Jan, Kravtsov Victor Ch., Filippova Irina G., Hauser Jürg, Speldrich Manfred, Hermann Raphaël P., Krämer Karl W., Liu Shi-Xia, Decurtins Silvio, Kögerler Paul, Baca Svetlana G.,
Project Dimensional and Anisotropy Control of Model Quantum Magnets
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Original article (peer-reviewed)

Journal Crystal Growth & Design
Volume (Issue) 14(9)
Page(s) 4721 - 4728
Title of proceedings Crystal Growth & Design
DOI 10.1021/cg5008236

Open Access

URL http://boris.unibe.ch/id/eprint/59680
Type of Open Access Repository (Green Open Access)

Abstract

Two new magnetic cluster-based 3D coordination polymers consisting of μ3-oxo-centered cationic homometallic [FeIII3O-(O2CCMe3)6]+ or neutral heterometallic [FeIII2CoIIO(O2CCMe3)6] coordination clusters bridged by different N,N′-donor ligands into three-dimensional networks of {[Fe3O(O2CCMe3)6(4,4′-bpy)1.5](OH)·0.75(CH2Cl2 ) · x(H2O)}n (1 , x ≈ 8) and {[Fe2CoO-(O2CCMe3)6(bpe)0.5(pyz)]}n (2) (where 4,4′-bpy = 4,4′-bipyridine; bpe = 1,2′-bis(4-pyridyl)ethylene; pyz = pyrazine) have been prepared under solvothermal conditions. Single-crystal X-ray diffraction studies reveal the existence of a 6-fold interpenetrated network with rare (8,3)-c (etc) topology for 1 and a 3-fold interpenetrated network with (10,3)-b (ths) topology for 2. The interpenetration effectively results in very low BET surface areas, and the compounds have to be regarded as nonporous. Magnetic studies of 1 and 2 point to both ferro- and antiferromagnetic intra- and intercluster exchange interactions between the isotropic FeIII and the strongly anisotropic CoII spin centers. 57Fe Mossbauer spectroscopy confirms the uniform ferric (+III) valence state in both 1 and 2, and low-temperature data for 1 point toward distinct hyperfine fields for the Fe sites.
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