Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 22, Issue 19, Pages 6564-6574Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201600202
Keywords
biopolymers; magnetic properties; metal-organic frameworks; polyoxometalates
Categories
Funding
- Ministere de l'Enseignement Superieur et de la Recherche
- CNRS
- Universite de Versailles Saint Quentin en Yvelines
- French National Research Agency (ANR) [ANR-11-IDEX-0003-02, CHARMMMAT ANR-11-LABX-0039]
- European Union [610449]
- ANR [ANR-13-BS10-0001-03 MolQuSpin]
- Labex CSC of the University of Strasbourg
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The chemically and structurally highly stable polyoxometalate (POM) single-molecule magnet (SMM) [(FeW9O34)(2)Fe-4(H2O)(2)](10-) (Fe6W18) has been incorporated by direct or post-synthetic approaches into a biopolymer gelatin (Gel) matrix and two crystalline metal-organic frameworks (MOFs), including one diamagnetic (UiO-67) and one magnetic (MIL-101(Cr)). Integrity of the POM in the Fe6W18@Gel, Fe6W18@UiO-67 and Fe6W18@MIL-101(Cr) composites was confirmed by a set of complementary techniques. Magnetic studies indicate that the POMs are magnetically well isolated. Remarkably, in Fe6W18@Gel, the SMM properties of the embedded molecules are close to those of the crystals, with clear quantum tunneling steps in the hysteresis loops. For the Fe6W18@UiO-67 composite, the molecules retain their SMM properties, the energy barrier being slightly reduced in comparison to the crystalline material and the molecules exhibiting a tunneling rate of magnetization significantly faster than for Fe6W18@Gel. When Fe6W18 is introduced into MIL-101(Cr), the width of the hysteresis loops is drastically reduced and the quantum tunneling steps are smeared out because of the magnetic interactions between the antiferromagnetic matrix and the SMM guest molecules.
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